TWI874681B - Polyisocyanate composition, film-forming composition, film, film laminate, adhesive resin composition and adhesive resin cured product, coating composition and coating cured product - Google Patents

Abstract

The present invention provides a polyisocyanate composition, etc., which has at least one isocyanate compound selected from the group consisting of aliphatic isocyanates and alicyclic isocyanates as a skeleton, the average value of the total number of isocyanate groups blocked by a blocking agent and isocyanate groups not blocked by a blocking agent in each molecule of the polyisocyanate is 2 or more, and 1 mol% or more and 99 mol% or less of the isocyanate groups in the polyisocyanate composition are blocked by a blocking agent.

Description

Polyisocyanate composition, film-forming composition, film, film laminate, adhesive resin composition and adhesive resin cured product, coating composition and coating cured product

The present invention relates to a polyisocyanate composition, a film-forming composition, a film, a film laminate, an adhesive resin composition and an adhesive resin cured product, and a coating composition and a coating cured product.

Polyisocyanate compositions obtained from aliphatic diisocyanates and cycloaliphatic diisocyanates have been widely used in various applications since ancient times due to their excellent weather resistance and heat resistance.

In addition, blocked polyisocyanate compositions that use blocking agents to block the isocyanate groups of polyisocyanate compositions can maintain their physical properties after curing and exhibit storage stability after mixing with active hydrogen compounds, so they are widely used as curing agents for automobile painting, etc.

Patent document 1 discloses an improved technology for using blocked polyisocyanates blocked with two blocking agents, pyrazole-based blocking agents and oxime-based blocking agents, as blocked polyisocyanate compositions in order to exhibit low-temperature curing properties and adhesion to various substrates. In addition, patent document 2 discloses a technology for using a curable adhesive composition of a polyisocyanate composition formed by mixing a blocked polyisocyanate compound with a non-blocked polyisocyanate compound as a combination that takes into account both crosslinking density and curing deformation.

However, in order to further demonstrate the performance of various urethane-based thermosetting compositions, further improvements to polyisocyanates or blocked polyisocyanates are expected.

As an example of an area that is expected to be improved, decorative films for interior and exterior parts of automobiles can be cited. As a method for decorating the surface of a three-dimensional substrate such as interior and exterior parts of automobiles, there is a known method of attaching a film having a design (hereinafter referred to as a "decorative film") to the surface of a substrate. As a representative method of attaching a film, a vacuum-pressure forming method can be cited. In the vacuum-pressure forming method, a decorative film is stretched at room temperature or in a heated environment with respect to a pre-formed substrate, while being attached to the substrate using a pressure difference. In this method, since the decorative film is attached to the substrate surface of the part in an operation different from the forming of the substrate, a vacuum-pressure forming device can be used to attach the decorative film to substrates of various materials and shapes. In molded products made of plastic, metal or other materials, the surface is usually decorated in order to give it a design or protect it.

As decorative films, laminated films such as those described in Patent Documents 3 and 4 are known. Decorative films used in vacuum-pressure forming require higher elongation. In addition, when decorative films are used on three-dimensional substrates represented by automotive exterior parts, not only elongation but also weather resistance and solvent resistance are required. However, in the technologies of Patent Documents 3 and 4, it is difficult to take into account both elongation and solvent resistance.

Furthermore, in the steps of film manufacturing, storage, and transportation, the film needs to be rolled up. At this time, there is a situation where the rolled films are attached to each other due to adhesion. Anti-adhesion performance that does not cause such problems is also required.

As another example of an area where improvement is expected, optical components can be cited. In recent years, because optical components are used under extremely harsh conditions, the expectation for adhesive resin compositions that can exert the properties of solvent resistance before lamination, adhesion of various functional layers used as the upper layer, and stability under high temperature and high humidity in the polyester film used in optical components has increased. Therefore, polyisocyanate compositions that can be used for such purposes and adhesive resin compositions using the same are expected.

Furthermore, in recent years, the curing agent in the two-component coating composition has also been required to have higher solvent resistance from the perspective of high functionality. In Patent Document 5, a polyisocyanate composition is provided in which the functional group number of isocyanate is increased in order to further promote the crosslinking of the coating composition. On the other hand, in the case of a two-component coating composition, it is expected that the coating can have a longer service life after the two liquids are prepared. In the above-mentioned coating composition, when the crosslinking of the coating film is increased, there is a tendency to have excellent solvent resistance, and when the functional group number is increased, there is a concern that the service life of the coating is shortened.

[Prior Art Literature] [Patent Literature]

[Patent document 1] Japanese Patent No. 5371884

[Patent Document 2] Japanese Patent Publication No. 2016-027153

[Patent Document 3] Japanese Patent Publication No. 2016-203434

[Patent Document 4] Japanese Patent Publication No. 2016-120642

[Patent Document 5] Japanese Patent Publication No. 2017-82076

By using the technology described in patent documents 3 and 4, a film with good elongation can be obtained. However, there has been no research on decorative films that not only have high elongation but also take into account solvent resistance and adhesion resistance. In addition, in the field of optical components, polyisocyanate compositions are required that can exert the properties of solvent resistance before lamination when making adhesive resin cured products, adhesion of various functional layers used as upper layers, and stability under high temperature and high humidity. Furthermore, from the perspective of high functionality of two-component coating compositions, polyisocyanate compositions that can take into account both higher solvent resistance of coatings and longer service life of coatings are expected.

The present invention is made in view of the above circumstances, and provides a polyisocyanate composition, a film-forming composition, a film, a film laminate, an adhesive resin composition and an adhesive resin cured product, a coating composition and a cured coating product using the polyisocyanate composition. When the polyisocyanate composition is used as a film-forming composition, the film has good elongation and excellent anti-blocking and solvent resistance. When the polyisocyanate composition is used as an adhesive resin composition, the film has excellent solvent resistance before lamination, excellent adhesion of various functional layers used as upper layers, and excellent stability under high temperature and high humidity. When the polyisocyanate composition is used as a coating composition, both the solvent resistance of the coating film and the service life of the coating can be taken into consideration.

That is, the present invention includes the following aspects.

[1] A polyisocyanate composition having at least one isocyanate compound selected from the group consisting of aliphatic isocyanates and alicyclic isocyanates as a skeleton, wherein the average total number of isocyanate groups blocked by a blocking agent and isocyanate groups not blocked by a blocking agent in each molecule of the polyisocyanate is 2 or more, and 1 mol% or more and 99 mol% or less of the isocyanate groups in the polyisocyanate composition are blocked by a blocking agent.

[2] A polyisocyanate composition as described in [1], wherein the average total number of isocyanate groups blocked by a blocking agent and isocyanate groups not blocked by a blocking agent in each molecule of the polyisocyanate is 3 or more.

[3] A polyisocyanate composition as described in [1] or [2], wherein the polyisocyanate composition comprises a polyisocyanate represented by the following general formula (I).

(In the general formula (I), R ¹¹ is a residue obtained by removing an isocyanate group from a polyisocyanate derived from the above-mentioned isocyanate compound; X ¹¹ is a structural unit derived from the above-mentioned end-capping agent; m and n are each independently any integer greater than 1, and n/(m+n) is greater than 0.01 and less than 0.99)

[4] A polyisocyanate composition as described in any one of [1] to [3], wherein 10 mol% or more and 90 mol% or less of the isocyanate groups in the polyisocyanate composition are blocked with a blocking agent.

[5] A film-forming composition comprising a polyisocyanate composition as described in any one of [1] to [4].

[6] A thin film forming composition as described in [5], which further contains a compound containing active hydrogen.

[7] A film-forming composition as described in [6], wherein the active hydrogen-containing compound comprises acrylic polyol.

[8] A composition for forming a thin film as described in [6], wherein the active hydrogen-containing compound comprises a diol.

[9] A thin film formed by hardening a thin film forming composition as described in any one of [5] to [8].

[10] A thin film laminate having at least two layers selected from the group consisting of a substrate layer, a decorative layer and a bonding layer, wherein at least one of the layers constituting the thin film laminate comprises the thin film described in [9].

[11] An article comprising the film as described in [9] or the film laminate as described in [10].

[12] The article as described in [11] is obtained by a manufacturing method comprising the following steps: heating the film as described in [9] or the film laminate as described in [10] while making it follow the article and adhere to the article; and then hardening the adhered film or film laminate.

[13] An adhesive resin composition comprising a polyisocyanate composition as described in any one of [1] to [4].

[14] A bonding resin composition as described in [13], which further contains a compound containing active hydrogen.

[15] A cured adhesive resin material obtained by curing the adhesive resin composition as described in [13] or "14".

[16] A method for manufacturing a laminate, comprising the following steps: applying an adhesive resin composition as described in [13] or [14] to at least one side of an adherend; and bonding the adherend coated with the adhesive resin composition to another adherend.

[17] The method for manufacturing a laminate as described in [16] further comprises the step of heating the adherends that have been bonded.

[18] A coating composition comprising a polyisocyanate composition as described in any one of [1] to [4].

[19] A coating composition as described in [18], which further contains a compound containing active hydrogen.

[20] A hardened paint product, which is obtained by hardening the paint composition as described in [18] or "19".

[21] A composite resin hardener comprising: a coating composition as described in [18] or [19]; and a metal, glass, plastic or wood component as a substrate.

[22] A method for producing a coating film, comprising the step of applying the coating composition as described in [18] or [19].

[23] A one-time curing film, which is formed by curing a polyisocyanate composition having at least one isocyanate compound selected from the group consisting of aliphatic isocyanates and alicyclic isocyanates as a skeleton and a compound containing active hydrogen, and comprises at least one functional group X selected from the group consisting of urethane groups, urea groups, and amide groups generated by curing the above-mentioned active hydrogen-containing compound and the above-mentioned polyisocyanate composition, an active hydrogen group, and an isocyanate group blocked by a blocking agent.

[24] A single-curing film as described in [23], wherein the ratio of the molar number γ of the functional group X contained in the single-curing film to the molar number β of the isocyanate group blocked by the blocking agent, i.e. γ/β, is greater than 0.1 and less than 9.0.

[25] A single-cured film as described in [23] or [24], wherein the molar number γ of the functional group X contained in 1 kg of the single-cured film is greater than 0.05 and less than 1.0.

[26] A single-curing film as described in any one of [23] to [25], wherein the compound containing active hydrogen comprises acrylic polyol.

[27] A single-curing film as described in any one of [23] to [26], wherein the active hydrogen-containing compound comprises a diol.

[28] A secondary hardened film, which is formed by further heating the primary hardened film as described in any one of [20] to [27] to harden it.

[29] A method for producing a secondary cured film, comprising the following steps: heating the primary cured film as described in any one of [23] to [27] at a temperature of not less than 50°C and not more than 140°C to follow and adhere to a molded body; and then heating the primary cured film at a temperature of not less than 50°C and not more than 180°C to cure the attached resin composition.

[30] A method for producing a secondary cured film as described in [29], wherein the ratio γ/γ' of the molar number γ of the functional group X contained in the primary cured film to the molar number γ' of the functional group X contained in the secondary cured film is greater than 0.1 and less than 0.9.

[31] A method for producing a secondary cured film as described in [29] or [30], wherein the molar number γ of the functional group X contained in 1 kg of the primary cured film is greater than 0.05 and less than 1.0, and the molar number γ' of the functional group X contained in 1 kg of the secondary cured film is greater than 0.5 and less than 10.

[32] A method for using a primary curing film, comprising the following steps: heating the primary curing film as described in any one of [23] to [27] at a temperature of not less than 50°C and not more than 140°C to follow and adhere to a molded article; and then heating the film at a temperature of not less than 50°C and not more than 180°C to cure the attached resin composition.

[33] A one-time curing film characterized by having a cross-linked structure and a curable functional group A.

[34] A film-forming composition, which can form a cross-linked structure of a once-cured film as described in [33], and contains a curable functional group A of a once-cured film as described in [33].

[35] A secondary hardened film, which is obtained by hardening the primary hardened film as described in [33].

[36] A method for manufacturing a secondary hardened film, comprising the following steps: heating the primary hardened film as described in [33] while allowing it to follow and adhere to a formed body; and then hardening the adhered resin composition.

[37] An article comprising a primary hardening film as described in [33] or a secondary hardening film as described in [34].

[38] An article comprising a secondary hardened film obtained by the manufacturing method described in [36].

According to the polyisocyanate composition of the above aspect, the following polyisocyanate composition can be provided. When the polyisocyanate composition is used as a film-forming composition, the film's elongation is well maintained, and the blocking resistance and solvent resistance are excellent. When used as an adhesive resin composition, the solvent resistance before lamination, the adhesion of various functional layers used as the upper layer, and the stability under high temperature and high humidity are excellent. When used as a coating composition, the solvent resistance of the coating film and the service life of the coating can be taken into account. According to the film-forming composition and the film of the above aspect, a film that maintains elongation well and has excellent blocking resistance and solvent resistance can be provided. The film laminate of the above aspect has a layer including the above film, and has excellent adhesion resistance and solvent resistance. According to the adhesive resin composition and the adhesive resin cured product of the above aspect, a kind of adhesive resin cured product with excellent solvent resistance before lamination, excellent adhesion of various functional layers used as the upper layer, and excellent stability under high temperature and high humidity can be provided. According to the coating composition and the coating cured product of the above aspect, a coating film with excellent solvent resistance and sufficient coating service life (hereinafter, sometimes referred to as "trial period") can be provided.

The present embodiment (hereinafter referred to as "the present embodiment") is described in detail below. The present embodiment below is an example for describing the present invention and is not intended to limit the present invention to the following contents. The present invention can be appropriately modified and implemented within the scope of its purpose.

In this specification, the term "polyisocyanate" refers to a polymer formed by combining multiple monomers having one or more isocyanate groups (-NCO).

In addition, in this specification, the so-called "polyol" means a compound having two or more hydroxyl groups (-OH).

Furthermore, unless otherwise specified, "(meth)acrylic acid" is considered to include methacrylic acid and acrylic acid.

≪Polyisocyanate composition≫

The polyisocyanate composition of this embodiment has at least one isocyanate compound selected from the group consisting of aliphatic isocyanates and alicyclic isocyanates as a skeleton.

The average value of the total number of isocyanate groups blocked by a blocking agent and isocyanate groups not blocked by a blocking agent per molecule of the polyisocyanate in the polyisocyanate composition (hereinafter, sometimes referred to as "the total average number of isocyanate groups") is 2 or more. The lower limit of the total average number of isocyanate groups is 2, preferably 2.3, more preferably 3, further preferably 3.4, and particularly preferably 4.5. On the other hand, the upper limit of the total average number of isocyanate groups is not particularly limited, but is preferably 20, more preferably 15, further preferably 10, and particularly preferably 8. That is, the total average number of isocyanate groups is 2 or more, preferably 2 or more and 20 or less, more preferably 2.3 or more and 15 or less, further preferably 3 or more and 10 or less, particularly preferably 3.4 or more and 10 or less, and most preferably 4.5 or more and 8 or less.

By making the total average number of isocyanate groups above the above lower limit, a film with further improved crosslinking properties and better blocking resistance and solvent resistance can be obtained. On the other hand, by making the total average number of isocyanate groups below the above upper limit, excessive crosslinking can be more effectively suppressed, thereby maintaining the elongation of the obtained film more effectively.

The total average number of isocyanate groups is calculated by the following formula. In the following formula, "Mn" is the number average molecular weight of the polyisocyanate composition measured after the blocking agent is decomposed by heating, etc. "NCO content" is the content of isocyanate groups relative to the total mass of the polyisocyanate composition measured after the blocking agent is decomposed by heating, etc. In addition, in order to convert the NCO content from a percentage to a decimal, the NCO content is multiplied by "0.01". "42" is the formula weight of isocyanate.

Total average number of isocyanate groups (total average number of NCO groups) = (Mn×NCO content×0.01)/42

Furthermore, the number average molecular weight (Mn) can be calculated, for example, by performing gel permeation chromatography (GPC) on the polyisocyanate composition. The NCO content can be calculated, for example, by using the polyisocyanate composition after the blocking agent is decomposed by heating as a sample and titrating it. Specifically, it can be calculated using the method shown in the following examples.

Alternatively, the total average number of isocyanate groups can be calculated by using the polyisocyanate composition as a sample and performing ¹³ C-NMR (Nuclear Magnetic Resonance) measurement.

Examples of polyisocyanates having a total average number of isocyanate groups within the above range include isocyanurate-type polyisocyanates obtained by trimerizing diisocyanate, biuret-type polyisocyanates formed by the reaction of three isocyanate group molecules with one water molecule, and allophanate-type polyisocyanates formed by the reaction of two isocyanate group molecules with one hydroxyl group molecule of an alcohol. Among them, from the perspective of weather resistance, isocyanurate-type polyisocyanates are preferred as polyisocyanates having a total average number of isocyanate groups within the above range.

The ratio of isocyanate groups blocked by a blocking agent in the isocyanate groups in the polyisocyanate composition (hereinafter sometimes referred to as "blocking ratio") is 1 mol% or more and 99 mol% or less.

When the polyisocyanate composition is used as a film-forming composition, the blocking rate is preferably 10 mol% or more and 90 mol% or less, more preferably 30 mol% or more and 90 mol% or less, further preferably 50 mol% or more and 80 mol% or less, and particularly preferably 50 mol% or more and 80 mol% or less.

By making the end-capping ratio above the above lower limit, the elongation of the obtained film can be better maintained. On the other hand, by making the end-capping ratio below the above upper limit, the operability of the obtained film at room temperature, that is, the anti-blocking property at room temperature, can be made better.

On the other hand, when the polyisocyanate composition is used as an adhesive resin composition, the end-capping rate is preferably 10 mol% or more and 90 mol% or less, preferably 20 mol% or more and 80 mol% or less, more preferably 30 mol% or more and 70 mol% or less, and particularly preferably 40 mol% or more and 60 mol% or less.

By making the blocking rate above the above lower limit, the adhesion to various functional layers used as the upper layer of the obtained adhesive resin cured product (hereinafter referred to as "adhesion to the upper layer") and the stability at high temperature and high humidity such as 80°C and 95%RH can be made better. On the other hand, by making the blocking rate below the above upper limit, the solvent resistance before laminating various functional layers on the obtained adhesive resin cured product (hereinafter referred to as "solvent resistance before lamination") can be made better.

On the other hand, when the polyisocyanate composition is used as a coating composition, the blocking rate is preferably 10 mol% or more and 90 mol% or less, more preferably 20 mol% or more and 85 mol% or less, and further preferably 30 mol% or more and 75 mol% or less. By making the blocking rate within the above range, the solvent resistance and low temperature drying properties of the obtained coating hardened material can be made better, and the trial period of the coating can be made longer. The content of the blocking rate can be measured using the method shown in the following embodiment.

The end-capping rate can be calculated, for example, using a titration method or the method shown in the following examples. Specifically, the end-capping rate can be calculated according to the following formula.

Capping rate = molar number of capping agent/molar number of isocyanate groups

Furthermore, the "isocyanate molar number" in the above formula is the isocyanate molar number per unit mass in the polyisocyanate composition after the end-capping agent is decomposed by heat treatment, and can be quantified using the NCO content and the following formula. Here, in order to convert the NCO content from a percentage to a decimal, the NCO content is multiplied by "0.01". "42" is the formula weight of isocyanate.

Isocyanate molar number = (NCO content × 0.01)/42

In addition, the "molar number of the end-capping agent" in the above formula can capture the end-capping agent when the end-capping agent is decomposed, and the molar number of the end-capping agent can be quantified by gas chromatography-mass spectrometry.

The polyisocyanate composition of this embodiment has the above-mentioned structure, and can provide an isocyanate composition that can maintain the elongation of the film well when used as a film-forming composition, and has excellent anti-blocking and solvent resistance. When used as an adhesive resin composition, it has excellent solvent resistance before lamination, and excellent adhesion of various functional layers used as the upper layer and stability under high temperature and high humidity. When used as a coating composition, it can take into account both the solvent resistance of the coating film and the service life of the coating.

The following is a detailed description of each component contained in the polyisocyanate composition of this embodiment.

The above-mentioned polyisocyanate composition includes a blocked polyisocyanate derived from a polyisocyanate and a blocking agent. The blocked polyisocyanate is a blocked polyisocyanate in which a part or all of the isocyanate groups in one molecule are blocked by a blocking agent. Hereinafter, a blocked polyisocyanate in which a part of the isocyanate groups in one molecule of the blocked polyisocyanate are blocked by a blocking agent is referred to as a "partially blocked polyisocyanate". In addition, a blocked polyisocyanate in which all of the isocyanate groups in one molecule of the blocked polyisocyanate are blocked by a blocking agent is referred to as a "wholly blocked polyisocyanate".

Furthermore, the above-mentioned polyisocyanate composition includes, in addition to blocked polyisocyanate, unblocked polyisocyanate (hereinafter, sometimes referred to as "unblocked polyisocyanate").

When the polyisocyanate composition contains only blocked polyisocyanate, the blocking rate can be controlled within the above range by using partially blocked polyisocyanate alone or by adjusting the mixing ratio of partially blocked polyisocyanate to the whole blocked polyisocyanate. On the other hand, when the polyisocyanate composition contains blocked polyisocyanate and unblocked polyisocyanate, the blocking rate can be controlled within the above range by adjusting the mixing ratio of partially blocked polyisocyanate or the whole blocked polyisocyanate to the unblocked polyisocyanate.

[Polyisocyanate]

二

三酮基、脲基、胺基甲酸酯基，較佳為具有異氰尿酸酯基。作為成為聚異氰酸酯之骨架之異氰酸酯化合物，並無特別限定，具體而言，較佳為其結構中不包含苯環等芳香族環者。 The polyisocyanate used as the raw material of the polyisocyanate composition is derived from at least one isocyanate compound selected from the group consisting of aliphatic isocyanates and alicyclic isocyanates, and has the skeleton of the isocyanate compound. The polyisocyanate may also contain isocyanurate groups, biuret groups, allophanate groups,

two

The isocyanate compound which is the backbone of the polyisocyanate is not particularly limited, but is preferably one which does not contain an aromatic ring such as a benzene ring in its structure.

(Aliphatic isocyanate)

The aliphatic isocyanate is not particularly limited, and specifically, examples thereof include aliphatic monoisocyanate, aliphatic diisocyanate, lysine triisocyanate, 4-isocyanatomethyl-1,8-octamethylene diisocyanate (trimer triisocyanate), etc. Among them, aliphatic diisocyanate is preferred.

There is no particular limitation on the aliphatic diisocyanate. Specifically, it is preferably one with a carbon number of 4 or more and 30 or less, such as tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (hereinafter referred to as "HDI"), 2,2,4-trimethyl-1,6-diisocyanatohexane, lysine diisocyanate, etc. Among them, HDI is preferred in terms of ease of industrial acquisition. The aliphatic diisocyanate may be used alone or in combination of two or more.

(Alicyclic isocyanate)

There is no particular limitation on the alicyclic isocyanate, and specific examples thereof include alicyclic monoisocyanate, alicyclic diisocyanate, etc. Among them, alicyclic diisocyanate is preferred.

烯二異氰酸酯、氫化苯二甲基二異氰酸酯等。其中，就耐候性、工業獲取之容易性之觀點而言，較佳為IPDI。脂環族二異氰酸酯可僅單獨使用1種，亦可將2種以上併用。 The alicyclic diisocyanate is not particularly limited, but preferably has a carbon number of 8 or more and 30 or less, and examples thereof include isophorone diisocyanate (hereinafter referred to as "IPDI"), 1,3-bis(isocyanatomethyl)-cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, and isophorone diisocyanate.

Among them, IPDI is preferred from the viewpoint of weather resistance and ease of industrial availability. The alicyclic diisocyanate may be used alone or in combination of two or more.

[Capping agent]

There is no particular limitation on the end-capping agent, and specifically, compounds having one active hydrogen in the molecule can be cited. There is no particular limitation on such end-capping agents, and specifically, examples include: alcohol compounds, alkanephenol compounds, phenol compounds, active methylene compounds, thiol compounds, amide compounds, imide compounds, imidazole compounds, urea compounds, oxime compounds, amine compounds, imine compounds, pyrazole compounds, and triazole compounds. Such end-capping agents can be used alone or in combination of two or more. More specific examples of end-capping agents are shown below.

There is no particular limitation on the alcohol compound, and specific examples thereof include methanol, ethanol, 2-propanol, n-butanol, sec-butanol, 2-ethyl-1-hexanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, etc.

There are no particular limitations on alkphenol compounds. Specifically, mono- and di-alkanophenols having an alkyl group with 3 or more and 12 carbon atoms as a substituent can be cited. Examples of mono-alkanophenols include n-propylphenol, isopropylphenol, n-butylphenol, sec-butylphenol, tert-butylphenol, n-hexylphenol, 2-ethylhexylphenol, n-octylphenol, and n-nonylphenol. Examples of di-alkanophenols include di-n-propylphenol, diisopropylphenol, isopropylcresol, di-n-butylphenol, di-tert-butylphenol, di-sec-butylphenol, di-n-octylphenol, di-2-ethylhexylphenol, and di-n-nonylphenol.

There is no particular limitation on the phenolic compound, and specific examples thereof include phenol, cresol, ethylphenol, styrenated phenol, hydroxybenzoate, etc.

There is no particular limitation on the active methylene compounds, and specific examples thereof include dimethyl malonate, diethyl malonate, diisopropyl malonate, methyl acetylacetate, ethyl acetylacetate, acetylacetone, ethyl isobutyrylacetate, etc.

There is no particular limitation on the thiol compound, but specific examples thereof include butyl mercaptan, dodecyl mercaptan, etc.

There is no particular limitation on the amide compounds, and specific examples thereof include acetaniline, acetamide, ε-caprolactam, δ-valerolactamide, γ-butyrolactam, etc.

There is no particular limitation on the imide compounds, and specific examples thereof include succinimide, butylenediimide, etc.

There is no particular limitation on the imidazole compound, and specific examples thereof include imidazole, 2-methylimidazole, etc.

There is no particular limitation on the urea compound, but specific examples thereof include urea, thiourea, and ethylene urea.

The oxime compounds are not particularly limited, and specifically, for example, formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime, etc. can be cited.

There is no particular limitation on the amine compound, and specific examples thereof include diphenylamine, aniline, carbazole, di-n-propylamine, diisopropylamine, isopropylethylamine, etc.

There is no particular limitation on the imine compound, and specific examples thereof include ethyleneimine, polyethyleneimine, etc.

There is no particular limitation on the pyrazole compound, and specific examples thereof include pyrazole, 3-methylpyrazole, 3,5-dimethylpyrazole, etc.

There is no particular limitation on the triazole compound, and specific examples thereof include 1,2,4-triazole, 1,2,3-triazole, etc.

Among them, in terms of the ease of obtaining or the viscosity, curing temperature and curing time of the obtained polyisocyanate composition, amide compounds, oxime compounds, active methylene compounds or pyrazole compounds are preferred. Moreover, in consideration of the ease of synthesis when a part of the isocyanate groups in the polyisocyanate composition remain, amide compounds, oxime compounds or pyrazole compounds are more preferred. Specifically, methyl ethyl ketone oxime, ε-caprolactam, diethyl malonate, 3-methylpyrazole or 3,5-dimethylpyrazole are preferred, methyl ethyl ketone oxime, ε-caprolactam, 3-methylpyrazole or 3,5-dimethylpyrazole are further preferred, methyl ethyl ketone oxime or 3,5-dimethylpyrazole are particularly preferred, and 3,5-dimethylpyrazole is the most preferred.

[Partially blocked polyisocyanate]

The polyisocyanate composition preferably comprises a partially blocked polyisocyanate represented by the following general formula (I) (hereinafter, sometimes referred to as "partially blocked polyisocyanate (I)").

(In the general formula (I), R ¹¹ is a residue obtained by removing an isocyanate group from a polyisocyanate derived from the above-mentioned isocyanate compound; X ¹¹ is a structural unit derived from the above-mentioned end-capping agent; m and n are each independently any integer greater than 1, and n/(m+n) is greater than 0.01 and less than 0.99)

Partially blocked polyisocyanate (I) is derived from polyisocyanate and a blocking agent, and a portion of the isocyanate groups in the blocked polyisocyanate 1 molecule is blocked by the blocking agent.

As shown in the general formula (I), the structural unit ^X11 derived from the blocking agent is bonded to R11 of the residue formed by removing the isocyanate group from the isocyanate compound through an ^amide bond formed by the reaction of the active hydrogen of the blocking agent with the isocyanate group.

(R ¹¹ )

二

三酮基、脲基、胺基甲酸酯基等。R¹¹中之烷基可單獨使用1種該等官能基，亦可將2種以上組合使用。 R ¹¹ is a residue obtained by removing an isocyanate group from a polyisocyanate derived from the above-mentioned isocyanate compound. That is, R ¹¹ is at least one alkyl group selected from the group consisting of an aliphatic alkyl group and an alicyclic alkyl group that may contain a specific functional group. Examples of the specific functional group include an isocyanurate group, a biuret group, an allophanate group,

two

triketone group, urea group, urethane group, etc. As the alkyl group in ^{R 11} , one type of these functional groups may be used alone, or two or more types may be used in combination.

(X ¹¹ )

X ¹¹ is a structural unit derived from the end-capping agent, and can also be called a residue formed by removing active hydrogen from the end-capping agent. As X ¹¹ , the same structural unit derived from the end-capping agent as exemplified in the above-mentioned "end-capping agent" can be cited. Among them, as X ¹¹ , it is preferably a structural unit derived from an amide compound, an oxime compound, an active methylene compound or a pyrazole compound. Moreover, it is more preferably a structural unit derived from an amide compound, an oxime compound or a pyrazole compound. Specifically, preferred are structural units derived from methyl ethyl ketone oxime, ε-caprolactam, diethyl malonate, 3-methylpyrazole or 3,5-dimethylpyrazole, further preferred are structural units derived from methyl ethyl ketone oxime, ε-caprolactam, 3-methylpyrazole or 3,5-dimethylpyrazole, particularly preferred are structural units derived from methyl ethyl ketone oxime or 3,5-dimethylpyrazole, and most preferred are structural units derived from 3,5-dimethylpyrazole.

(m and n)

m represents the number of isocyanate groups in the partially blocked polyisocyanate (I) 1 molecule that are not blocked by a blocking agent. n represents the number of isocyanate groups in the partially blocked polyisocyanate (I) 1 molecule that are blocked by a blocking agent.

m and n are each independently any integer greater than 1, and n/(m+n) is greater than 0.01 and less than 0.99. From the perspective of cross-linking, m is preferably greater than 2.

"n/(m+n)" is the ratio of the number of isocyanate groups blocked by a blocking agent in the partially blocked polyisocyanate (I) 1 molecule to the total number of isocyanate groups not blocked by a blocking agent and the number of isocyanate groups blocked by a blocking agent.

When the polyisocyanate composition is used as a film-forming composition, n/(m+n) is 0.01 or more and 0.99 or less, preferably 0.10 or more and 0.90 or less, more preferably 0.30 or more and 0.90 or less, further preferably 0.50 or more and 0.90 or less, and particularly preferably 0.50 or more and 0.80 or less.

Furthermore, when the polyisocyanate composition is used as the adhesive resin composition, n/(m+n) is 0.01 or more and 0.99 or less, preferably 0.10 or more and 0.90 or less, more preferably 0.20 or more and 0.80 or less, further preferably 0.30 or more and 0.70 or less, and particularly preferably 0.40 or more and 0.60 or less.

Furthermore, when the polyisocyanate composition is used as a coating composition, n/(m+n) is greater than 0.01 and less than 0.99, preferably greater than 0.10 and less than 0.90, more preferably greater than 0.20 and less than 0.85, and further preferably greater than 0.30 and less than 0.75.

As a preferred partially blocked polyisocyanate (I), for example, the partially blocked polyisocyanate represented by the following general formula (I-1) can be cited.

(In the general formula (I-1), ^R12 is the same as ^R11 above; m1 and n1 are the same as m and n above, respectively)

When the polyisocyanate composition of the present embodiment is used as a film-forming composition, the content of the partially blocked polyisocyanate relative to the total molar amount of the partially blocked polyisocyanate, the whole blocked polyisocyanate and the unblocked polyisocyanate can be set to 0 mol% or more and 100 mol% or less, preferably 10 mol% or more and 90 mol% or less, more preferably 30 mol% or more and 90 mol% or less, further preferably 50 mol% or more and 90 mol% or less, and particularly preferably 50 mol% or more and 80 mol% or less.

By keeping the content of partially blocked polyisocyanate within the above range, the elongation of the obtained film can be better maintained.

Furthermore, when the polyisocyanate composition of the present embodiment is used as an adhesive resin composition, the content of the partially blocked polyisocyanate relative to the total molar amount of the partially blocked polyisocyanate, the whole blocked polyisocyanate and the unblocked polyisocyanate can be set to 0 mol% or more and 100 mol% or less, preferably 10 mol% or more and 90 mol% or less, more preferably 20 mol% or more and 80 mol% or less, further preferably 30 mol% or more and 70 mol% or less, and particularly preferably 40 mol% or more and 60 mol% or less.

By keeping the content of partially blocked polyisocyanate within the above range, the solvent resistance before lamination, the adhesion to the upper layer, and the stability under high temperature and high humidity can be improved when making the adhesive resin cured product.

Furthermore, when the polyisocyanate composition of the present embodiment is used as a coating composition, the content of the partially blocked polyisocyanate relative to the total molar amount of the partially blocked polyisocyanate, the whole blocked polyisocyanate and the unblocked polyisocyanate can be set to 0 mol% or more and 100 mol% or less, preferably 10 mol% or more and 90 mol% or less, more preferably 20 mol% or more and 85 mol% or less, and further preferably 30 mol% or more and 75 mol% or less.

By keeping the content of partially blocked polyisocyanate within the above range, the solvent resistance and low-temperature curing properties of the obtained cured coating can be improved, and the trial period of the coating can be extended.

The content of partially blocked polyisocyanate can be measured using the method shown in the following example.

[Method for producing polyisocyanate composition]

The polyisocyanate composition can be prepared by reacting a polyisocyanate with a blocking agent.

As methods for producing polyisocyanate compositions, the following two methods can be cited, for example.

(1) A method for producing a polyisocyanate composition containing only partially blocked polyisocyanate by reacting a blocking agent in an amount of 0.01 times or more and 0.99 times or less of the molar number of isocyanate groups in the polyisocyanate; (2) A method for producing a polyisocyanate composition by mixing a whole blocked polyisocyanate in which all isocyanate groups of the polyisocyanate are blocked by a blocking agent with at least one of an unblocked polyisocyanate and a partially blocked polyisocyanate.

As a method for producing a polyisocyanate composition, the target polyisocyanate composition can be obtained by using any of the above methods. In terms of being able to better demonstrate the elongation of the obtained film and the solvent resistance before lamination when making a cured adhesive resin, the above method (1) is preferred.

The reaction between polyisocyanate and blocking agent can be carried out by known methods, with or without solvent. When a solvent is used, a solvent that is inert to isocyanate groups must be used. In addition, a catalyst can be used as needed.

Examples of solvents include esters, ketones, and aromatic compounds. Examples of esters include ethyl acetate and butyl acetate. Examples of ketones include methyl ethyl ketone. Examples of aromatic compounds include toluene and xylene.

Examples of catalysts include organic metal salts, tertiary ammonium salts, alkali metal alkoxides, etc. Examples of metals used as organic metal salts include tin, zinc, lead, etc. Examples of alkali metals include sodium, etc.

The lower limit of the reaction temperature of polyisocyanate and end-capping agents such as pyrazole compounds is generally 20°C, preferably 0°C, and more preferably 30°C. On the other hand, the upper limit of the reaction temperature is 150°C, preferably 120°C, and more preferably 100°C.

That is, the reaction temperature is above -20°C and below 150°C, preferably above 0°C and below 120°C, and more preferably above 30°C and below 100°C.

By keeping the reaction temperature within the above range, side reactions can be reduced and the reaction can be carried out at an appropriate reaction rate.

≪Thin film forming composition≫

The film-forming composition of this embodiment contains the following component 1) or component 1) and 2).

1) Polyisocyanate composition described in “Polyisocyanate composition”; 2) Compounds containing active hydrogen

The film-forming composition according to this embodiment can provide a film (hereinafter sometimes referred to as a "primary curing film") that maintains good elongation and has excellent anti-blocking and solvent resistance by containing the above-mentioned polyisocyanate composition.

<Compounds containing active hydrogen>

There is no particular limitation on the active hydrogen-containing compound. Specifically, it is preferably a compound having two or more active hydrogens bonded in the molecule. Preferred active hydrogen-containing compounds include, for example, polyol compounds, polyamine compounds, alkanolamine compounds, polythiol compounds, etc. Among them, polyol compounds are preferred in terms of obtaining a film that maintains good elongation and has excellent weather resistance and solvent resistance.

[Polyol compounds]

There is no particular limitation on the polyol compound, and specifically, polyester polyol, acrylic polyol, polyether polyol, polyolefin polyol, fluorine polyol, polycarbonate polyol, epoxy resin, etc. Among them, as a polyol compound, acrylic polyol, polyester polyol, polyether polyol or polycarbonate polyol is preferred, and acrylic polyol is more preferred in terms of obtaining a film that maintains good elongation and has excellent weather resistance and solvent resistance.

(Polyester polyol)

As a polyester polyol, for example, it can be obtained by condensing a single dibasic acid or a mixture with a single polyol or a mixture.

Examples of the above-mentioned dibasic acid include succinic acid, adipic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid and other carboxylic acids.

Examples of the above-mentioned polyols include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, trimethylpentanediol, cyclohexanediol, trihydroxymethylpropane, glycerol, pentaerythritol, 2-hydroxymethylpropanediol, ethoxylated trihydroxymethylpropane, etc.

As a specific method for producing polyester polyol, for example, the following method can be cited: the above components are mixed, and then heated at a temperature of about 160°C or more and 220°C or less to perform a condensation reaction.

Or as a method for producing polyester polyols, specifically, for example, a method of using polyols to perform ring-opening polymerization on lactones such as ε-caprolactone to obtain polycaprolactones such as polycaprolactone diol, and the obtained polycaprolactones can be used as polyester polyols.

The polyester polyols can be modified with aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and polyisocyanates obtained therefrom. In this case, aliphatic diisocyanates, alicyclic diisocyanates, and polyisocyanates obtained therefrom are particularly preferred from the viewpoints of weather resistance and yellowing resistance.

When used as a composition for forming a water-based film, a portion of the residual dibasic acid or a portion of the carboxylic acid is allowed to remain in advance and neutralized with a base such as amine or ammonia to produce a water-soluble or water-dispersible resin.

(Acrylic polyol)

There is no particular limitation on the acrylic polyol. Specifically, for example, a single compound or mixture of a monomer containing an ethylenically unsaturated bond having a hydroxyl group and a copolymer of a single compound or mixture of another monomer containing an ethylenically unsaturated bond copolymerizable therewith can be cited.

The monomer having an ethylenically unsaturated bond and having a hydroxyl group is not particularly limited, and specifically, examples thereof include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, etc. Among them, hydroxyethyl acrylate or hydroxyethyl methacrylate is preferred.

As other monomers containing ethylenic unsaturated bonds that can be copolymerized with the above-mentioned monomers, for example: (meth)acrylates, unsaturated carboxylic acids, unsaturated amides, vinyl monomers having hydrolyzable silyl groups, other polymerizable monomers, etc. These monomers can be used alone or in combination of two or more.

Examples of the above-mentioned (meth)acrylates include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, glycidyl methacrylate, etc.

Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, itaconic acid, etc.

Examples of unsaturated amides include acrylamide, N-hydroxymethyl acrylamide, diacetone acrylamide, etc.

Examples of vinyl monomers having a hydrolyzable silyl group include vinyl trimethoxysilane, vinyl methyl dimethoxysilane, and γ-(meth)acryloyl propyl trimethoxysilane.

As other polymerizable monomers, for example, styrene, vinyl toluene, vinyl acetate, acrylonitrile, dibutyl fumarate, etc. can be cited.

For example, the above-mentioned monomer components can be subjected to solution polymerization in the presence of a known free radical polymerization initiator such as a peroxide or azo compound, and then diluted with an organic solvent as needed to obtain an acrylic polyol.

When obtaining a water-based acrylic polyol, it can be produced by a known method such as a solution polymerization of an ethylenic unsaturated compound and conversion to an aqueous layer or emulsion polymerization. In this case, the acidic part of a carboxylic acid-containing monomer such as acrylic acid or methacrylic acid or a sulfonic acid-containing monomer can be neutralized with amines or ammonia to impart water solubility or water dispersibility.

(Polyether polyol)

There is no particular limitation on polyether polyols. Specifically, they include: polyether polyols obtained by adding a single compound or a mixture of alkylene oxide to a single compound or a mixture of polyhydroxy compounds in the presence of a strong alkaline catalyst; polyether polyols obtained by reacting alkylene oxide with polyfunctional compounds such as ethylenediamine; and so-called polymer polyols obtained by polymerizing acrylamide and the like using these polyethers as a medium.

Examples of the above-mentioned polyhydroxy compounds include diglycerol, di-trihydroxymethylpropane, pentaerythritol, dipentaerythritol, sugar alcohol compounds, monosaccharides, disaccharides, trisaccharides, and tetrasaccharides.

Examples of the sugar alcohol compound include erythritol, D-threitol, L-arabitol, ribitol, xylitol, sorbitol, mannitol, galactitol, and rhamnitol .

Examples of monosaccharides include arabinose, ribose, xylose, glucose, mannose, galactose, fructose, sorbose, rhamnose, fucose, deoxyribose, etc.

Examples of disaccharides include trehalose, sucrose, maltose, cellobiose, gentianbiose, lactose, melibiose, etc.

Examples of trisaccharides include raffinose, gentianatriose, and raffinose.

Examples of tetrasaccharides include stachyose and the like.

There is no particular limitation on the strong alkaline catalyst. Specifically, examples include: hydroxides of alkaline metals such as lithium, sodium, and potassium; alcohol salts, alkylamines, etc.

Examples of the above-mentioned alkylene oxides include ethylene oxide, propylene oxide, butylene oxide, hexylene oxide, styrene oxide, etc.

(Polyolefin polyol)

The polyolefin polyol is not particularly limited, and specifically, polybutadiene, hydrogenated polybutadiene, polyisoprene, and hydrogenated polyisoprene having two or more hydroxyl groups can be cited.

(Fluoropolyol)

The so-called fluorinated polyol is a polyol containing fluorine in the molecule, for example, copolymers of fluoroolefins, cyclovinyl ethers, hydroxyalkyl vinyl ethers, and vinyl monocarboxylates disclosed in Japanese Patent Publication No. 57-34107 (reference 1) and Japanese Patent Publication No. 61-275311 (reference 2), etc.

(Polycarbonate polyol)

There is no particular limitation on the polycarbonate polyol. Specifically, examples include those obtained by polycondensing a low molecular carbonate compound with the polyol used in the polyester polyol. There is no particular limitation on the low molecular carbonate compound. Specifically, examples include: dialkyl carbonates such as dimethyl carbonate; alkyl carbonates such as ethylene carbonate; diaryl carbonates such as diphenyl carbonate, etc.

(Epoxy)

The epoxy resin is not particularly limited, and specifically, examples thereof include novolac epoxy resins, glycidyl ether epoxy resins, glycol ether epoxy resins, aliphatic unsaturated compound epoxy resins, epoxy fatty acid esters, polycarboxylic acid ester epoxy resins, aminoglycidyl epoxy resins, β-methylepichlorohydrin epoxy resins, oxirane epoxy resins, halogen epoxy resins, and resorcinol epoxy resins.

(Hydroxyl value)

The hydroxyl value of the polyol compound is preferably 5 mgKOH/g or more and 600 mgKOH/g or less, more preferably 10 mgKOH/g or more and 500 mgKOH/g or less, and further preferably 15 mgKOH/g or more and 400 mgKOH/g or less, in terms of crosslinking density and mechanical properties of the film. In addition, the acid value of the polyol compound is preferably 0 mgKOH/g or more and 30 mgKOH/g or less. The hydroxyl value and acid value can be obtained based on titration.

[Polyamine compounds]

、2-甲基哌

、異佛爾酮二胺等。作為具有3個以上胺基之鏈狀多胺類，例如可例舉：雙六亞甲基三胺、二伸乙基三胺、三伸乙基四胺、四伸乙基五胺、六亞甲基六胺、四伸丙基五胺等。作為環狀多胺類，例如可例舉：1,4,7,10,13,16-六氮雜環十八烷、1,4,7,10-四氮雜環癸烷、1,4,8,12-四氮雜環十五烷、1,4,8,11-四氮雜環十四烷等。 The polyamine compound is not particularly limited, and specifically, for example, diamines, chain polyamines having three or more amino groups, and cyclic polyamines can be cited. Examples of the diamines include ethylenediamine, propylenediamine, butylenediamine, triethylenediamine, hexamethylenediamine, 4,4'-diaminodicyclohexylmethane, piperidine, and the like.

, 2-methylpiperidin

, isophoronediamine, etc. Examples of chain polyamines having three or more amino groups include dihexamethylenetriamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenehexamine, and tetrapropylpentamine. Examples of cyclic polyamines include 1,4,7,10,13,16-hexaazacyclooctadecane, 1,4,7,10-tetraazacyclodecane, 1,4,8,12-tetraazacyclopentadecane, and 1,4,8,11-tetraazacyclotetradecane.

[Alkanolamine compounds]

There is no particular limitation on the alkanolamine compound, and specific examples thereof include monoethanolamine, diethanolamine, aminoethylethanolamine, N-(2-hydroxypropyl)ethylenediamine, mono-, di-(n- or iso-)propanolamine, ethylene glycol-bis-propylamine, neopentanolamine, methylethanolamine, etc.

[Polythiol compounds]

There is no particular limitation on the polythiol compound, but specific examples thereof include bis-(2-hydrothioethoxy)methane, dithioethylene glycol, dithioerythritol, dithiothreitol, etc.

The active hydrogen-containing compounds may be used alone or in combination of two or more. Among them, as active hydrogen-containing compounds, it is preferred to use acrylic polyol alone or in combination with acrylic polyol and diol in order to obtain a film that maintains good elongation and has excellent weather resistance and solvent resistance. The "diol" referred to here refers to a compound having two hydroxyl groups among the above-mentioned polyol compounds. There is no particular limitation on "diol", and specifically, examples include: compounds having two hydroxyl groups among the polyols or polycaprolactones listed in the above-mentioned "polyester polyols", and compounds having two hydroxyl groups among the above-mentioned "polycarbonate polyols".

[NCO/OH]

When the active hydrogen-containing compound is a polyol compound, the molar ratio (NCO/OH) of the isocyanate (-NCO) group of the polyisocyanate composition relative to the hydroxyl group (-OH) of the polyol compound is preferably 0.2 or more and 5.0 or less, more preferably 0.4 or more and 3.0 or less, and further preferably 0.5 or more and 2.0 or less. By making NCO/OH above the lower limit, there is a tendency to obtain a tougher film. By making NCO/OH below the upper limit, there is a tendency to further improve the smoothness of the obtained film. Furthermore, the molar number of "isocyanate (-NCO) groups in the polyisocyanate composition" used in the calculation of NCO/OH is the total molar number of isocyanate groups not blocked by a blocking agent and isocyanate groups blocked by a blocking agent.

<Other additives>

The film-forming composition of this embodiment may contain various additives such as organic solvents, hardening-accelerating catalysts, antioxidants, ultraviolet absorbers, light stabilizers, pigments, levelers, plasticizers, surfactants, etc. according to the purpose and use.

As an organic solvent, it is preferred that it does not have a functional group that reacts with a hydroxyl group and an isocyanate group, and it is preferred that it is fully compatible with the polyisocyanate composition. Such an organic solvent is not particularly limited, and for example, it can be a solvent commonly used as a coating solvent, and examples thereof include: ester compounds, ether compounds, ketone compounds, aromatic compounds, ethylene glycol dialkyl ether compounds, polyethylene glycol dicarboxylate compounds, hydrocarbon solvents, etc.

The hardening accelerating catalyst is not particularly limited, and specifically, for example, tin compounds, zinc compounds, titanium compounds, cobalt compounds, bismuth compounds, zirconium compounds, amine compounds, etc. Examples of tin compounds include dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, dimethyltin dineodecanoate, bis(2-ethylhexanoate)tin, etc. Examples of zinc compounds include zinc 2-ethylhexanoate, zinc cycloalkanoate, etc. Examples of titanium compounds include titanium 2-ethylhexanoate, titanium diisopropylate (ethyl acetate), etc. Examples of cobalt compounds include cobalt 2-ethylhexanoate and cobalt cycloalkanoate. Examples of bismuth compounds include bismuth 2-ethylhexanoate and bismuth cycloalkanoate. Examples of zirconium compounds include magnesium tetraacetylpyruvate, zirconium 2-ethylhexanoate, and zirconium cycloalkanoate.

There is no particular limitation on the antioxidant, but specific examples include hindered phenol compounds, phosphorus compounds, sulfur compounds, etc.

系化合物、二苯甲酮系化合物等。 The ultraviolet absorber is not particularly limited, and specifically, for example, benzotriazole compounds,

Series compounds, benzophenone series compounds, etc.

系化合物、二苯甲酮系化合物、苯甲酸酯系化合物等。 The light stabilizer is not particularly limited, and specific examples thereof include hindered amine compounds, benzotriazole compounds,

Series compounds, benzophenone series compounds, benzoate series compounds, etc.

There is no particular limitation on the pigments, but specific examples include titanium oxide, carbon black, indigo, pearl mica, aluminum, etc.

There is no particular limitation on the leveling agent, but specifically, silicone oil and the like can be cited as examples.

There is no particular limitation on the plasticizer, and specific examples include phthalates, phosphoric acid compounds, polyester compounds, etc.

There is no particular limitation on the surfactant, and specifically, examples thereof include: well-known anionic surfactants, cationic surfactants, amphoteric surfactants, etc.

<Method for producing a composition for forming a thin film>

When the film-forming composition of the present embodiment is an organic solvent-based composition, for example, the above-mentioned polyisocyanate composition is first added as a curing agent to a compound containing active hydrogen or a solvent dilution thereof, and other additives such as resins, catalysts, pigments, leveling agents, antioxidants, ultraviolet absorbers, light stabilizers, plasticizers, and surfactants are added as needed. Then, an organic solvent is further added as needed to adjust the viscosity. Then, by manually stirring or using a stirring machine such as Mazera, a film-forming composition with an organic solvent base can be obtained.

When the film-forming composition of the present embodiment is a water-based matrix, for example, firstly, a curing agent, other resins, catalysts, pigments, leveling agents, antioxidants, ultraviolet absorbers, light stabilizers, plasticizers, surfactants and other additives that can react with the crosslinking functional groups in the active hydrogen-containing compound are added to the active hydrogen-containing compound or its aqueous dispersion or water-soluble substance as needed. Then, the above-mentioned polyisocyanate composition or its aqueous dispersion is added as a curing agent, and water or solvent is further added as needed to adjust the viscosity. Then, the film-forming composition of the water-based matrix is obtained by forced stirring by a stirring machine.

≪Primary curing film F1 and secondary curing film F2≫

The one-time cured film of this embodiment is formed by curing a polyisocyanate composition having at least one isocyanate compound selected from the group consisting of aliphatic isocyanates and alicyclic isocyanates as a skeleton and a compound containing active hydrogen, and contains at least one functional group X selected from the group consisting of urethane groups, urea groups, and amide groups generated by curing the above-mentioned active hydrogen-containing compound and the above-mentioned polyisocyanate composition, an active hydrogen group, and an isocyanate group blocked by a blocking agent.

The once-cured film of this embodiment is formed by curing the above-mentioned film-forming composition. The once-cured film of this embodiment maintains good elongation and has excellent anti-blocking properties.

The primary cured film of this embodiment is obtained by applying the above-mentioned film forming composition to a substrate and curing it at room temperature or after heating. Specifically, the isocyanate group of the polyisocyanate composition in the film forming composition reacts with the active hydrogen of the compound containing active hydrogen to form a primary cured film. At this time, the blocked isocyanate group is directly maintained, thereby showing good elongation when the primary cured film is attached. In addition, after the primary cured film is attached to various substrates, it is heated again to dissociate the blocking agent bonded to the isocyanate group, thereby forming a crosslink. Through the formation of the crosslink, a secondary cured film with improved crosslinking density of the film and showing weather resistance and solvent resistance can be obtained.

As coating methods, there are known methods such as reverse roll coating, gravure coating, contact coating, die nozzle coating, roll brush coating, spray coating, air knife coating, wire rod coating, tubular scraper coating, impregnation coating, curtain coating, roll coating, curtain flat coating, spray coating, bell coating, and electrostatic coating.

The thickness of the primary cured film is not particularly limited, but is preferably 0.2 μm or more and 500 μm or less, more preferably 1 μm or more and 500 μm or less, further preferably 5 μm or more and 300 μm or less, and particularly preferably 5 μm or more and 100 μm or less.

In the preparation of the primary cured film and the secondary cured film in the present embodiment, a film forming composition comprising the above-mentioned polyisocyanate composition and a compound containing active hydrogen is preferred. By using the above-mentioned film forming composition, a primary cured film comprising a cross-linked structure formed by the reaction of an isocyanate group and an active hydrogen group, an active hydrogen group, and an isocyanate group blocked by a blocking agent can be obtained. The cross-linked structure contained in the primary cured film can make the operability of the obtained film at room temperature, that is, the anti-adhesion property at room temperature, better. In addition, the primary cured film can be further cross-linked by the active hydrogen group contained in the primary cured film and the isocyanate group blocked by a blocking agent, thereby obtaining a secondary cured film with excellent solvent resistance.

The functional group (hereinafter referred to as functional group X) that forms the cross-linked structure by the reaction of isocyanate group and active hydrogen group is not particularly limited, and preferably includes at least one selected from carbamate group, urea group, and amide group.

In the primary cured film of this embodiment, the ratio of the molar number γ of the functional group X contained in 1 kg of the primary cured film to the molar number β of the isocyanate group blocked by the blocking agent, i.e., γ/β, can be set to 0.02 or more and 9.0 or less. γ/β is preferably set to 0.1 or more and 2.4 or less, more preferably 0.1 or more and 1.0 or less, and particularly preferably 0.2 or more and 1.0 or less. By setting γ/β to a value above the lower limit, the operability of the obtained film at room temperature, i.e., the anti-blocking property at room temperature, can be made better. On the other hand, by setting γ/β to a value below the upper limit, the elongation of the film can be better maintained.

Furthermore, in the primary cured film of the present embodiment, the ratio of the molar number γ of the functional group X contained in 1 kg of the primary cured film to the molar number α of the active hydrogen group, i.e., γ/α, can be set to be greater than 0.1 and less than 9.0. γ/α is preferably set to be greater than 0.1 and less than 2.4, more preferably greater than 0.1 and less than 1.0, and particularly preferably greater than 0.2 and less than 1.0.

In the primary cured film of this embodiment, the ratio of the molar number β of the isocyanate groups blocked by the blocking agent to the molar number α of the active hydrogen groups contained in 1 kg of the primary cured film, i.e., β/α, can be set to be greater than 0.02 and less than 20. β/α is preferably set to be greater than 0.1 and less than 10, more preferably greater than 0.2 and less than 5.0, and particularly preferably greater than 0.5 and less than 2.0.

In addition, the ratio of the molar number γ of the functional group X contained in 1 kg of the primary cured film to the molar number γ' of the functional group X contained in 1 kg of the secondary cured film, i.e., γ/γ', can be set to be greater than 0.1 and less than 0.9. γ/γ' is preferably greater than 0.1 and less than 0.7, more preferably greater than 0.1 and less than 0.5, and particularly preferably greater than 0.2 and less than 0.5. By setting γ/γ' to a value greater than the lower limit, the operability of the obtained film at room temperature, i.e., the anti-blocking property at room temperature, can be made better. On the other hand, by setting γ/γ' to a value less than the upper limit, the elongation of the film can be better maintained.

The characteristic of the primary cured film in this embodiment is that the molar number γ of the functional group X contained in 1 kg of the primary cured film and the molar number γ' of the functional group X contained in 1 kg of the secondary cured film are respectively within the following ranges.

1) The molar number γ of the functional group X contained in 1 kg of the primary cured film is greater than 0.05 and less than 1.0. γ is preferably greater than 0.05 and less than 0.8, more preferably greater than 0.07 and less than 0.6, and particularly preferably greater than 0.1 and less than 0.4. By making γ greater than the lower limit, a self-supporting film having a certain crosslinking density can be obtained. On the other hand, by making γ less than the upper limit, the elongation of the primary cured film can be maintained.

2) The molar number γ' of the functional group X contained in 1 kg of the secondary cured film is greater than 0.3 and less than 10. γ' is preferably greater than 0.3 and less than 5.0, more preferably greater than 0.5 and less than 2.0, and particularly preferably greater than 0.5 and less than 1.2. By setting γ' to a value greater than the lower limit, the crosslinking density of the secondary cured film is increased, showing solvent resistance. In addition, by setting γ' to a value less than the upper limit, the mechanical properties of the secondary cured film can be well maintained.

In this embodiment, the tensile modulus of the once-cured film can be obtained by using the stress-strain curve when the measuring temperature is set to the glass transition temperature of the film + 10°C and the stretching speed is set to 100%/min. The tensile modulus of the once-cured film is preferably 0.1 MPa or more and 3.0 MPa or less when the slope is calculated by setting the stress and deformation to a linear relationship in the elongation range of 5% to 10%. By making the tensile modulus below the upper limit, good elongation can be obtained, and by making the tensile modulus above the lower limit, the strength of the film required during stretching can be maintained. The tensile modulus is preferably 0.2 MPa or more and 1.5 MPa or less, more preferably 0.3 MPa or more and 1.1 MPa or less, and even more preferably 0.4 MPa or more and 0.7 MPa or less.

<How to use the one-time curing film F1>

As described above, the primary curing film of this embodiment can be attached to the surface of a pre-formed substrate, or can be attached to the surface while forming an object using a known forming method. Next, by further heating the formed body to which the primary curing film is attached to harden the attached primary curing film, a formed body protected by a film having high solvent resistance can be obtained.

The film can be attached to the surface of the substrate using a known attachment method. Specific examples of the former include vacuum forming, pressure forming, vacuum-pressure forming, lamination, etc. Specific examples of the latter include in-mold forming, film embedding, etc.

Among them, it is preferably used in vacuum-pressure forming, in-mold forming, and film embedding forming, which require particularly high elongation. It is even better to use it in vacuum-pressure forming for film attachment regardless of the material as long as it is a pre-formed substrate.

There is no particular limitation on the method of attaching the primary curing film. From the perspective of the film's followability to the molded body, it is preferred to heat the primary curing film at a temperature of 50°C or higher and 140°C or lower while allowing it to follow the molded body and adhere to the molded body. By setting the heating temperature to a value above the lower limit, the film can further follow the molded body and adhere to the molded body. In addition, by setting the heating temperature to a value below the upper limit, the dissociation of the isocyanate groups blocked by the blocking agent contained in the primary curing film can be prevented.

The heating temperature for further curing the attached primary cured film is preferably set to be above 50°C and below 180°C. The heating temperature is preferably above 50°C and below 170°C, more preferably above 50°C and below 160°C, and particularly preferably above 100°C and below 150°C. By setting the heating temperature to the above range, the isocyanate groups blocked by the blocking agent are dissociated and react with active hydrogen groups to form a cross-linked film with high solvent resistance.

≪Primary curing film F1' and secondary curing film F2'≫

The one-time curing film of this embodiment includes a cross-linking structure and a curable functional group A. By having a cross-linking structure, the film has the strength of a self-supporting film and exhibits the operability of the film, that is, the anti-adhesion property. Furthermore, since the functional group A is included, the film can be cured after being attached. Even if the cross-linking density is lower than the level that well exhibits the elongation of the film when attached, the weather resistance and solvent resistance of the final film can be ensured.

As described above, the primary cured film F1' in this embodiment is obtained by applying the film forming composition to a substrate and applying an external stimulus to cure it. At this time, a part of the reactive functional groups contained therein is retained in a residual state, thereby showing good extensibility when the film is attached. Next, by applying an external stimulus to the primary cured film, the reactive functional groups retained in the primary cured film are further cured, thereby obtaining a secondary cured film.

The crosslinking structure contained in the primary cured film F1' is not particularly limited, and may be formed by using known crosslinking reactions such as condensation, re-addition, and various polymerization reactions. Specifically, examples include: crosslinking by polymerization of compounds having carbon unsaturated bonds represented by vinyl and (meth) acrylic groups, crosslinking by ring-opening polymerization of cyclic compounds represented by ethylene oxide, crosslinking via amide bonds (polyamide), crosslinking via ester bonds (polyester), crosslinking via melamine bonds (melamine resin), crosslinking via carbonate bonds (polycarbonate), crosslinking via tert-butyl ether bonds (tert-butyl ether bonds), crosslinking via quaternary ether bonds (quaternary ... Crosslinking through urethane bonds (polyurethane), crosslinking through urea bonds (polyurea), crosslinking through polysilicone bonds (polysilicone resin), crosslinking through condensation of phenol and formaldehyde (phenol resin), crosslinking through condensation of urea and formaldehyde (urea resin), crosslinking through reaction of epoxy resin and hardeners such as amine, amide, acid, and anhydride, crosslinking through imide bonds (polyaniline), etc. Among them, crosslinking through urethane bonds, crosslinking through urea bonds, crosslinking through amide bonds, and crosslinking through polymerization of (meth) acrylic acid groups are preferred, and crosslinking through urethane bonds is particularly preferred.

Similarly, there is no particular limitation on the curable functional group A contained in the primary curing film, as long as it contains the functional groups required for the known curing reaction. Therefore, the functional group A can be single, or if necessary, it can contain multiple functional groups. Specifically, as functional groups that can undergo a curing reaction even if they are single, there can be cited: vinyl or (meth) acrylic acid group, silanol group, etc. Among them, (meth) acrylic acid group is preferred.

In addition, as a combination of functional groups that utilize multiple functional groups to perform a curing reaction, examples include: "active hydrogen and isocyanate", "carboxyl and hydroxyl", "epoxy and amine or acid, acid anhydride", "amine and formyl (aldehyde)", etc. Among them, the combination of "active hydrogen and isocyanate" is preferred.

Furthermore, the cross-linking structure formed by the cross-linking structure and the functional group A contained in the primary cured film may be the same or different.

Furthermore, the compound having a curable functional group A may be a compound without a reactive functional group, or a compound that is reactive when the following external stimulus is applied. These are also not particularly limited, and examples include: acid anhydride or blocked isocyanate compounds, etc.

When forming the cross-linked structure, it is carried out at room temperature or by applying some external stimulus. As specific types of external stimuli, there can be cited: heating, active energy ray irradiation, moisture, vibration, electric field, magnetic field, pressure, pH value change, etc. When forming the cross-linked structure contained in the primary hardened film, from the perspective of versatility and productivity of engineering equipment, heating, active energy ray irradiation, and moisture-based are preferred, and heating and active energy ray irradiation are more preferred, and heating is further preferred.

Furthermore, when forming a cross-linked structure by the functional group A, from the perspective of the method of use, it is more desirable not to perform cross-linking formation while the film is stored. Furthermore, from the perspective of cross-linking formation after being attached to a structure, in order to efficiently form the cross-linked structure, it is preferably performed by heating or irradiation with active energy rays.

The secondary cured film is obtained by reacting the curable functional group A contained in the primary cured film.

The cross-linking density of the film is increased through the reaction of functional group A, showing weather resistance and solvent resistance.

<Thin film forming composition>

The film-forming composition of this embodiment is characterized in that it contains a compound having a cross-linked structure or a compound that can form a cross-linked structure, and the above-mentioned curable functional group A. By applying the film-forming composition to a substrate and applying external stimulation such as heating as needed, a primary cured film containing a cross-linked structure and a curable functional group A is obtained.

<How to use the one-time curing film F1'>

The primary curing film of this embodiment is used by attaching it to the surface of a pre-formed substrate or by attaching it to the surface while forming an object using a known forming method. Next, by further heating the formed body to which the primary curing film is attached to harden the attached primary curing film, an object protected by a film having high solvent resistance can be obtained.

Regarding the attachment of the film, it is sufficient to attach the film to the surface of the substrate using a known method. The method is not particularly limited, and examples thereof include vacuum forming, pressure forming, vacuum-pressure forming, and lamination methods of attaching the film to a pre-formed substrate. In addition, as a method of attaching the film simultaneously with forming, examples thereof include in-mold forming, film embedding forming, etc.

Among them, it is preferably used in vacuum-pressure forming, in-mold forming, and film embedding forming, which require particularly high elongation. It is more preferably used in vacuum-pressure forming, which can be used for film attachment regardless of the material as long as the substrate is pre-formed.

≪Thin film laminate≫

The thin film laminate of this embodiment is a thin film laminate having at least two layers selected from the group consisting of a base layer, a decorative layer and a bonding layer. At least one layer of the layers constituting the thin film laminate includes the above-mentioned primary curing film F1 or F1'. The thin film laminate of this embodiment has excellent anti-adhesion and solvent resistance.

The thin film laminate of this embodiment may include the above-mentioned thin film in any one of the base layer and the decorative layer, or in both layers. Furthermore, the thin film laminate of this embodiment may include one layer (single layer) of the above-mentioned thin film in one layer constituting the thin film laminate, or may include more than two layers.

<Decorative layer>

There is no particular limitation on the decorative layer. Specifically, it can be exemplified by: a coloring layer, a pattern layer, etc. The decorative layer may include one layer (single layer) or may include two or more layers. When the decorative layer includes multiple layers, the composition, shape and thickness of the multiple layers may be the same or different. The combination of the multiple layers is not particularly limited as long as it does not impair the effect of the present invention.

Furthermore, in this specification, when not limited to the case of decorative layers, the phrase "multiple layers may be the same or different from each other" means "all layers may be the same, all layers may be different, or only some layers may be the same", and the phrase "multiple layers may be different from each other" means "at least one of the composition, shape, and thickness of each layer is different from each other".

The thickness of the decorative layer is not particularly limited, but is preferably greater than 0.2 μm and less than 100 μm. Furthermore, the "thickness of the decorative layer" mentioned here refers to the thickness of the decorative layer as a whole. For example, the thickness of a decorative layer comprising multiple layers refers to the total thickness of all layers constituting the decorative layer.

[Coloring layer]

系顏料、喹吖酮系顏料等。作為酞菁系顏料，例如可例舉：酞菁藍、酞菁綠等。作為喹吖酮系顏料，例如可例舉喹吖啶酮紅等。作為鋁發光材，例如可例舉：鋁片、蒸鍍鋁片、金屬氧化物被覆鋁片、著色鋁片等。作為分散於黏合劑樹脂中之顏料，例如可例舉：經氧化鈦、氧化鐵等金屬氧化物被覆之薄片狀之雲母及合成雲母等珍珠發光材 等。作為供顏料分散之黏合劑樹脂，例如可例舉：丙烯酸系樹脂、聚胺基甲酸酯樹脂等。 The so-called coloring layer is a layer showing a coating color, a metallic color, etc. Examples of the coloring agent contained in the coloring layer include: inorganic pigments, organic pigments, aluminum luminescent materials, pigments dispersed in a binder resin, and printing inks. Examples of inorganic pigments include: titanium oxide, carbon black, chromium yellow, yellow iron oxide, red iron oxide, and the like. Examples of organic pigments include: phthalocyanine pigments, azo pigments, indigo pigments, peroxycyclic pigments, perylene pigments, quinophthalone pigments, diisocyanate pigments, and the like.

Examples of the pigment include phthalocyanine blue, phthalocyanine green, and the like. Examples of the quinacridone pigment include quinacridone red, and the like. Examples of the aluminum luminescent material include aluminum sheets, vapor-deposited aluminum sheets, aluminum sheets coated with metal oxides, and colored aluminum sheets. Examples of the pigment dispersed in the binder resin include pearl luminescent materials such as mica and synthetic mica coated with metal oxides such as titanium oxide and iron oxide. Examples of the binder resin for the pigment to be dispersed include acrylic resins and polyurethane resins.

[Pattern layer]

The so-called pattern layer is a layer that gives patterns such as wood grain, geometric pattern, leather pattern, logo and pattern to the object. There is no particular limitation on the method for forming the pattern layer. Specifically, examples include known printing methods, known coating methods, punching, etching, etc. Examples of printing methods include: gravure direct printing, gravure offset printing, inkjet printing, laser printing, screen printing, etc. Examples of coating methods include: gravure coating, roller coating, die nozzle coating, rod coating, doctor blade coating, etc.

Furthermore, the material of the pattern layer may be a film containing the above-mentioned film-forming composition, or a film or sheet containing other resins or a metal foil.

<Base layer>

The base layer serves as a support layer for the decorative layer, and can also function as a protective layer that imparts uniform elongation during molding and more effectively protects the structure from damage such as punctures and impacts from the outside. The base layer may include one layer (single layer) or multiple layers of two or more. When the base layer includes multiple layers, the composition, shape, and thickness of the multiple layers may be the same or different, and the combination of the multiple layers is not particularly limited as long as it does not impair the effect of the present invention.

The substrate layer is not particularly limited, and examples thereof include: a layer formed of materials such as resin, metal (steel plate, surface treated steel plate, etc.), wood, inorganic material (glass, etc.), or a layer formed of the above-mentioned film-forming composition. As resins, examples thereof include: acrylic resins including polymethyl methacrylate, polyurethane, polyvinyl chloride, polycarbonate, polyolefin, polyester, acrylonitrile-butadiene-styrene copolymer, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, etc. As polyolefins, examples thereof include: polyethylene, polypropylene, etc. As polyesters, examples thereof include: polyethylene terephthalate, polyethylene naphthalate, etc.

The thickness of the substrate layer is not particularly limited. From the perspective of not adversely affecting the formability of the decorative layer and imparting the functions of the substrate layer to the film, it is preferably 2 μm or more and 500 μm or less, and more preferably 5 μm or more and 200 μm or less. Furthermore, the "thickness of the substrate layer" mentioned here refers to the thickness of the entire substrate layer. For example, the thickness of a substrate layer comprising multiple layers refers to the total thickness of all layers constituting the substrate layer.

<Next layer>

The thin film laminate of this embodiment may also have a bonding layer between the base layer and the decorative layer or between the base layer and the decorative layer when the base layer and the decorative layer include multiple layers. The bonding layer may include one layer (single layer) or may include multiple layers of two or more. When the bonding layer includes multiple layers, the composition, shape and thickness of the multiple layers may be the same or different, and the combination of the multiple layers is not particularly limited as long as it does not impair the effect of the present invention.

The adhesive contained in the adhesive layer is not particularly limited as long as it is a commonly used adhesive. Specifically, for example, solvent-type, emulsion-type, pressure-sensitive, heat-sensitive, thermosetting or UV-curing adhesives such as acrylic, polyolefin, polyurethane, polyester, and rubber can be cited.

The thickness of the bonding layer is not particularly limited. From the perspective of not adversely affecting the formability of the decorative layer and imparting the function of the above-mentioned base layer to the film, it is preferably 2 μm or more and 200 μm or less, and more preferably 5 μm or more and 100 μm or less. Furthermore, the "thickness of the bonding layer" mentioned here means the thickness of the bonding layer as a whole. For example, the thickness of a bonding layer including multiple layers means the total thickness of all layers constituting the bonding layer.

≪Adhesive resin composition≫

The adhesive resin composition of this embodiment contains the following component 1) or components 1) and 2).

1) The polyisocyanate composition described in the above-mentioned “polyisocyanate composition”; 2) Compounds containing active hydrogen

According to the adhesive resin composition of this embodiment, by containing the above-mentioned polyisocyanate composition, a cured adhesive resin having excellent solvent resistance before lamination, adhesion of various functional layers used as the upper layer, and stability under high temperature and high humidity can be provided. The "cured adhesive resin" referred to here is formed by curing the adhesive resin composition of this embodiment. That is, in one embodiment, the present invention provides a cured adhesive resin formed by curing the above-mentioned adhesive resin composition.

<Compounds containing active hydrogen>

As the active hydrogen-containing compound, it is as described in the above <Active hydrogen-containing compound>.

Furthermore, the adhesive resin composition of this embodiment may contain other crosslinking agent components in addition to the above-mentioned polyisocyanate composition.

<Other crosslinking agent ingredients>

唑啉化合物、三聚氰胺化合物、碳二醯亞胺化合物等。 As other crosslinking agent components, for example, epoxy compounds,

Oxazoline compounds, melamine compounds, carbodiimide compounds, etc.

As the epoxy compound, there is no particular limitation as long as it is a resin having two or more epoxy groups in one molecule, and known epoxy compounds can be used. Examples of epoxy compounds include: bisphenol-type epoxy compounds obtained by adding epichlorohydrin to bisphenol, novolac-type epoxy compounds obtained by adding epichlorohydrin to a phenolic novolac-type resin, and polyethylene glycol diglycidyl ether. The epoxy compound can be used after being dispersed in water as needed.

唑啉化合物，可例舉：側鏈具有至少2個

唑啉基之聚合物狀之化合物、1分子中具有至少2個

唑啉基之單體之化合物等。 As

Azoline compounds may include: a side chain having at least 2

A polymeric compound of an oxazoline group, having at least 2

Compounds of oxazoline monomers, etc.

As melamine compounds, for example, partially or completely hydroxymethylated melamine resins obtained by the reaction of melamine and aldehydes can be cited. As the above-mentioned aldehydes, for example, formaldehyde, paraformaldehyde, etc. can be cited. In addition, hydroxymethylated melamine resins obtained by partially or completely etherifying the hydroxymethyl groups of the hydroxymethylated melamine resins with alcohols can also be used. As examples of alcohols used for etherification, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-ethylbutanol, 2-ethylhexanol, etc. can be cited.

Specific examples of the melamine compound include Cymel 303, Cymel 323, Cymel 325, Cymel 327, Cymel 350, Cymel 370, Cymel 380, Cymel 385, Cymel 212, Cymel 251, Cymel 254, Micoat 776 (all of which are trade names) manufactured by Cytec Industries of Japan.

As a carbodiimide compound, for example, it can be obtained by allowing the isocyanate groups of a polyisocyanate compound to undergo a decarbonation reaction. Commercially available products of carbodiimide compounds include, for example, Carbodilite V-02, Carbodilite V-02-L2, Carbodilite V-04, Carbodilite E-01, and Carbodilite E-02 (all manufactured by Nisshin Textile Co., Ltd., trade names), etc.

The adhesive resin composition of this embodiment can be used in the form of a coating liquid diluted with various solvents, water, etc., in terms of workability and ease of film formation when applied to an adherend. As a solvent that can be used, for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, esters such as ethyl acetate, acetic acid-n-butyl ester, and acetic acid cellulose can be appropriately selected and used according to the purpose and use. These solvents can be used alone or in combination of two or more.

The solid content concentration of the adhesive resin composition of this embodiment is not particularly limited. It is preferably 10% by mass or more and 80% by mass or less, more preferably 15% by mass or more and 60% by mass or less, further preferably 20% by mass or more and 50% by mass or less, and particularly preferably 25% by mass or more and 40% by mass or less, relative to the total mass of the adhesive resin composition.

<Purpose of use>

As the application fields of the adhesive resin composition of this embodiment, there can be cited: automobiles, building materials or home appliances, woodworking, laminates for solar cells, etc. Among them, optical components for LCD displays of home appliances such as televisions, computers, digital phasers, mobile phones, etc. must laminate various films and flat plates of various adherends in order to exhibit various functions. In terms of requiring sufficient adhesion between the films and flat plates of various adherends, it is a better application example of the adhesive resin composition of this embodiment.

[Adhesion]

Examples of adherends that can be used with the adhesive resin composition of the present embodiment include: various metals such as glass, aluminum, iron, zinc steel plate, copper, and stainless steel; porous components such as mortar and stone; components coated with fluorine, urethane, and acrylic urethane; cured sealants such as silicone, modified silicone, and urethane; rubbers such as vinyl chloride, natural rubber, and synthetic rubber; films and plates of resins such as polyester, acrylic, polycarbonate, triacetyl cellulose, and polyolefin; UV-curable acrylic resin layers; layers containing inks such as printing inks and UV (ultraviolet) inks, etc. Among them, preferred are films and flat sheets of resins such as polyester, acrylic acid, polycarbonate, triacetyl cellulose, and polyolefin, or UV-curable acrylic resin layers.

The following describes the case where the adherend is a polyester film as an example.

As the polyester resin constituting the polyester film that can be used as the adherend of the adhesive resin composition of the present embodiment, for example, there can be mentioned polyester resins obtained by copolymerizing polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polymethylene naphthalate, and a copolymer component such as diol components such as diethylene glycol, neopentyl glycol, and polyalkylene glycol, or adipic acid components such as adipic acid, sebacic acid, phthalic acid, isophthalic acid, and 2,6-naphthalene dicarboxylic acid. Among them, as the polyester resin, it is preferred that at least one selected from the group consisting of polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate is used as a main component. Furthermore, among these polyester resins, polyethylene terephthalate is the best in terms of the balance between physical properties and cost. In addition, in terms of improving the chemical resistance, heat resistance, mechanical strength, etc. of these polyester films or polyester flat sheets, it is better to be biaxially stretched.

In addition, various additives may be added to the polyester resin as needed. Examples of additives include antioxidants, organic lubricants, antistatic agents, ultraviolet absorbers, surfactants, etc.

In order to obtain the required strength when used as an optical component, the thickness of the polyester film is preferably 10 μm or more and 400 μm or less, more preferably 20 μm or more and 300 μm or less, and further preferably 30 μm or more and 200 μm or less. In addition, the thickness of the polyester flat plate is not particularly limited, but is preferably 1 mm or more and 10 mm or less, more preferably 2 mm or more and 8 mm or less, and further preferably 3 mm or more and 5 mm or less. In this specification, the thickness is used to distinguish between films and flat plates, and those with a thickness of 500 μm or less are defined as films, and those with a thickness of more than 500 μm are defined as flat plates.

<How to use the adhesive resin composition>

The method of using the adhesive resin composition of this embodiment is described.

As a method of using the adhesive resin composition of the present invention, for example, a method including the following steps can be cited: a step of applying the adhesive resin composition of the present embodiment to at least one side of an adherend; a step of bonding the adherend coated with the adhesive resin composition to another adherend; and a step of heating the laminate formed by bonding the adherends as needed to bond them.

In addition, in the use of laminated films for optical components, the following methods can be cited as examples: the adhesive composition of this embodiment for the easy-to-bond layer is applied to a polyester film or the like to be an adherend in advance, and after a heat treatment step, another adherend is bonded; or the adhesive resin composition of this embodiment is applied to a film provided with an easy-to-bond layer and then bonded. The adhesive resin composition of this embodiment is effective when used by any of these methods.

Any known method can be used to apply the coating liquid containing the adhesive resin composition of the present embodiment to a film, etc. For example, roller coating, gravure coating, roller brush coating, spray coating, air knife coating, curtain coating, etc. These methods can be used alone or in combination.

The amount of coating liquid applied is not particularly limited. The thickness after drying is preferably 0.01 μm or more and 1 μm or less, more preferably 0.02 μm or more and 0.5 μm or less, and further preferably 0.04 μm or more and 0.3 μm or less.

In addition, inorganic particles such as silica and talc, and organic particles such as acrylic, urethane, and polyester can also be mixed into the coating liquid. Furthermore, surfactants, defoaming agents, preservatives, antistatic agents, etc. can also be mixed into the coating liquid.

The following is an explanation of the method for forming a coating layer, taking the case of making a polyester film that is easy to process as an example.

The adhesive resin composition of this embodiment is used as a crosslinking agent component for an easy-to-bond treatment layer (i.e., an adhesive layer pre-formed on a film substrate for bonding with an adherend) coated on the surface of a polyester film in order to improve the adhesion between the polyester film and various adherends. For example, when used for easy-to-bond treatment of a polyester film, the easy-to-bond treatment layer is mainly formed by the following two methods. The first is an in-line coating method in which a coating liquid containing necessary components is coated on a base film before crystallization alignment is completed, dried, and then extended in at least one axial direction, followed by heat treatment to complete the alignment of the polyester film. The second is an off-line coating method in which a coating liquid is applied to the polyester film after the film is manufactured and then dried. Generally speaking, in terms of manufacturing efficiency in which the coating layer is formed simultaneously with the manufacture of the polyester film, the in-line coating method is preferred.

(Method for manufacturing polyester film that is easy to process)

The method for producing an easily bondable polyester film by making the adhesive resin composition of this embodiment into an easily bondable layer is described.

First, the polyester constituting the film is melt-extruded into a film shape, and then cooled and solidified to obtain an unstretched polyester film. The biaxially stretched polyester film is made by stretching the unstretched film at Tg~(Tg+50)℃ to a length of more than 3 times and less than 5 times, and then stretching it at Tg~(Tg+50)℃ to a width of more than 3 times and less than 5 times, or stretching it in both the length and width directions, and then performing a heat treatment step at a temperature of more than 140℃ and less than 230℃ for more than 1 second and less than 60 seconds to complete.

Previously, the heat history in the heat treatment step lasted about 1 minute at 200°C, but from the perspective of protecting the global environment and improving productivity, it is expected that the heat treatment step will be lowered in temperature. Therefore, it is being studied to lower the temperature to about 1 minute at 150°C as the heat history. When the previous adhesive composition is used as an easy-to-bond treatment layer, there is a case where the initial adhesion and the adhesion after the wet heat resistance test are reduced. Therefore, even in the heat treatment step at a lower temperature, there is a strong demand for an adhesive composition that can show initial adhesion and adhesion after the wet heat resistance test. In order to show adhesion in the heat treatment step at 150°C for about 1 minute, it is better to form crosslinks at a lower temperature than the blocked polyisocyanate. Specifically, a crosslinking agent that can crosslink at a temperature below 60°C (starts the crosslinking reaction at a temperature below 60°C) is preferred.

The formation of the easily bondable polyester film by coating the adhesive resin composition of this embodiment can be implemented at any stage. It is preferred to apply the coating liquid before stretching or after one-axis stretching and dry it, then stretch it in at least one axis direction, and then perform heat treatment to complete it. In addition, the coating liquid can be applied only on one side, and there is no special problem in implementing it on both sides.

≪Coating composition≫

The coating composition of this embodiment contains the following component 1) or components 1) and 2).

1) The polyisocyanate composition described in the above-mentioned “polyisocyanate composition”; 2) Compounds containing active hydrogen

According to the coating composition of this embodiment, a coating cured product can be provided, which has excellent solvent resistance of the coating film and good coating test period due to the inclusion of the above-mentioned polyisocyanate composition. The "cured coating product" referred to here is the product obtained by curing the coating composition of this embodiment. That is, in one embodiment, the present invention provides a coating cured product obtained by curing the above-mentioned coating composition.

<Compounds containing active hydrogen>

As the active hydrogen-containing compound, it is as described in the above <Active hydrogen-containing compound>.

Furthermore, the coating composition of this embodiment may contain other crosslinking agent components in addition to the above-mentioned polyisocyanate composition.

<Other crosslinking agent ingredients>

As other crosslinking agent components, as described in the above <Other crosslinking agent components>.

The coating composition of this embodiment can be used in the form of a coating liquid diluted with various solvents, water, etc., in terms of workability and ease of thin film formation when applied to the coated object. As the solvent that can be used, for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, esters such as ethyl acetate, acetic acid-n-butyl ester, and acetic acid cellulose can be appropriately selected and used according to the purpose and use. These solvents can be used alone or in combination of two or more.

There is no particular restriction on the solid content concentration of the coating composition. In terms of ease of viscosity adjustment, it is preferably 10% by mass or more and 90% by mass or less, more preferably 25% by mass or more and 80% by mass or less, further preferably 35% by mass or more and 75% by mass or less, and particularly preferably 40% by mass or more and 70% by mass or less, relative to the total mass of the coating composition.

The coating composition can be calcined under any temperature conditions to promote curing. As a trend in recent years, in terms of reducing the heat energy in the equipment, a coating composition that cures at a lower temperature is required. As for the calcination temperature, from the perspective of excellent curing at low temperatures, it is preferably in the range of 40°C or more and 200°C or less, more preferably 60°C or more and 180°C or less, further preferably 80°C or more and 160°C or less, and particularly preferably 100°C or more and 140°C or less. By setting the calcination temperature in the above range, a coating film with excellent low-temperature drying properties and solvent resistance can be obtained.

<Purpose of use>

The coating composition of this embodiment is not limited to the following, for example, it can be preferably used as a base coating, intermediate coating or surface coating coating for coating on various materials formed by coating methods such as roller coating, curtain coating, spray coating, electrostatic coating, bell coating, etc. In addition, it is also effective as a coating for imparting cosmetic properties, weather resistance, acid resistance, rust resistance, and chip resistance to pre-coated metals including rustproof steel plates, automobiles, and plastic coatings. In addition, it is also effective as a urethane raw material for adhesives, elastomers, foams, surface treatment agents, etc. Examples of application areas of the coating composition of this embodiment include: automobiles, building materials or home appliances, woodworking, laminates for solar cells, etc.

[Painted objects]

Examples of the materials to be coated by the coating composition include: glass; various metals such as aluminum, iron, zinc steel plate, copper, stainless steel, etc.; porous components such as wood, paper, mortar, stone, etc.; components that have been coated with fluorine coating, urethane coating, acrylic urethane coating, etc.; sealants such as polysilicone-based cured products, modified polysilicone-based cured products, and urethane-based cured products. Materials; rubbers such as vinyl chloride, natural rubber, and synthetic rubber; leathers such as natural leather and artificial leather; fibers such as plant fibers, animal fibers, carbon fibers, and glass fibers; films and flat sheets of resins such as non-woven fabrics, polyester, acrylic, polycarbonate, triacetyl cellulose, and polyolefins; UV-curable acrylic resin layers; layers containing printing inks, UV inks, and other inks, etc.

[Implementation example]

The present embodiment is further described in detail below based on the embodiments and comparative examples, but the present embodiment is not limited by the following embodiments. Furthermore, unless otherwise specified, "%" and "parts" in the text refer to the mass standard.

The following shows the method for measuring the physical properties of the polyisocyanate composition obtained in the synthesis example, and the method for evaluating the thin film and thin film laminate obtained in the examples and comparative examples.

<Measurement and evaluation methods of physical properties> [Physical property 1] Viscosity

The measurement was performed using an Emila type rotational viscometer at 25°C.

[Physical property 2] Number average molecular weight

The number average molecular weight is the number average molecular weight based on polystyrene measured by gel permeation chromatography (GPC) using the following apparatus. A polyisocyanate composition is used as a sample. The measurement conditions are shown below.

(Measurement conditions)

Device: Tosoh Co., Ltd., HLC-802A

Column: Made by Tosoh Co., Ltd., G1000HXL × 1

G2000HXL×1

G3000HXL×1

Carrier: Tetrahydrofuran

Testing method: differential refractometer

[Physical Property 3] Isocyanate group (NCO) content

The isocyanate group (NCO) content is determined using the following method. When the polyisocyanate composition contains blocked polyisocyanate, the blocking agent is decomposed by heating or the like and then used as a measurement sample.

First, accurately weigh more than 2g and less than 3g of the polyisocyanate composition and place it in a flask (Wg). Then, add 20mL of toluene to dissolve the polyisocyanate composition after the end-blocking agent is dissolved. Then, add 20mL of a toluene solution of di-n-butylamine at a 2-equivalent concentration and mix, and then place it at room temperature for 15 minutes. Then, add 70mL of isopropanol and mix. Then, titrate the solution with a 1-equivalent hydrochloric acid solution (factor F) into the indicator. The obtained titration value is set to V2 mL. Then, perform the same operation in the absence of the polyisocyanate composition, and set the obtained titration value to V1 ml. Next, the isocyanate group (NCO) content of the polyisocyanate composition after the blocking agent is decomposed (isocyanate group (NCO) content) X1 (mass %) is calculated according to the following formula.

Isocyanate group (NCO) content X1 (mass %) = (V1-V2)×F×42/(W×1000)×100

[Physical Property 4] Total average number of isocyanate groups

The total average number of isocyanate groups (total average number of NCO) is obtained by the following formula. In the following formula, when the polyisocyanate composition contains blocked polyisocyanate, "Mn" is the number average molecular weight of the polyisocyanate composition measured after the blocking agent is decomposed by heating, etc. When the polyisocyanate composition contains blocked polyisocyanate, "NCO content" is the content of the isocyanate groups present relative to the total mass of the polyisocyanate composition measured after the blocking agent is decomposed by heating, etc., and is used for X1 (mass %) calculated in the above "Physical Property 3". In addition, in order to convert the NCO content from a percentage to a decimal, the NCO content is multiplied by "0.01". "42" is the formula weight of isocyanate.

Total average NCO = (Mn × NCO content (X1) × 0.01) / 42

[Physical Property 5] Capping Rate

The blocking ratio in the polyisocyanate composition and the film-forming composition is calculated according to the following formula.

Capping rate = molar number of capping agent/molar number of isocyanate groups

Furthermore, the "isocyanate molar number" in the above formula is the isocyanate molar number per unit mass in the polyisocyanate composition after the blocking agent is decomposed by heat treatment, and is quantitatively determined using the following formula using the NCO content (X1) calculated in the above "Physical Property 3". Here, in order to convert the NCO content (X1) from a percentage to a decimal, the NCO content (X1) is multiplied by "0.01". "42" is the formula weight of isocyanate.

Isocyanate molar number = (X1×0.01)/42

In addition, the "molar number of the end-capping agent" in the above formula is the end-capping agent captured when the end-capping agent is decomposed, and the molar number of the end-capping agent is quantified by gas chromatography-mass spectrometry.

[Physical Property 6] Content of partially blocked polyisocyanate

The content of partially blocked polyisocyanate is determined by the following LC-MS (Liquid Chromatography-Mass Spectrometry) and calculated based on the ratio of peak heights using the formula shown below.

Content of partially blocked polyisocyanate = [(peak B+peak C)/(peak A+peak B+peak C+peak D]×100

(Preprocessing)

Prepare a methanol solution (10 mg/mL) of the polyisocyanate composition and allow to stand for 1 day.

(Using machine)

．LC: 1100series manufactured by Agilent

．MS: LCQ manufactured by ThermoElectron

． Column: Phenomenex, Kinetex 2.6μm XB-C18 100 A (2.1mm I.D.×50mm)

(LC test conditions)

．Column temperature: 40℃

．Detection: 205nm

．Flow rate: 0.35mL/min

． Mobile phase: Mobile phase A uses 0.05% formic acid aqueous solution, and mobile phase B uses methanol.

． Gradient conditions: at 0 minutes, mobile phase A/mobile phase B = 50/50, at 30 minutes, mobile phase A/mobile phase B = 0/100, at 30.1 minutes, mobile phase A/mobile phase B = 50/50, at 42 minutes, mobile phase A/mobile phase B = 50/50).

．Injection volume: 2μLMS

(MS conditions)

． Ionization: APCI (Atmospheric Pressure Chemical Ionization method)

． Mode: Positive

．Scanning range: m/Z=250~2000

(Measurement results)

In this measurement, the following peaks A to D were detected in the retention time range of 16.4 to 18.4 minutes in the form of uncapped isocyanate groups and methanol addition.

． Peak A: In the case of uncapped polyisocyanate trimer, methanol is added to three isocyanate groups and detected as peak A with a molecular weight of 600.

． Peak B: In the case of a single-terminated polyisocyanate trimer, methanol is added to two of the three isocyanate groups to obtain a peak in the form of a blocking agent added to one isocyanate group. When the blocking agent is 3,5-dimethylpyrazole, it is detected as a peak B with a molecular weight of 664.

． Peak C: In the case of di-blocked polyisocyanate trimer, methanol is added to one of the three isocyanate groups to obtain a peak in the form of the blocking agent added to two isocyanate groups. When the blocking agent is 3,5-dimethylpyrazole, it is detected as a peak C with a molecular weight of 728.

． Peak D: The fully blocked polyisocyanate (overall blocked polyisocyanate) trimer is formed by adding a blocking agent to three isocyanate groups. When the blocking agent is 3,5-dimethylpyrazole, it is detected as a peak D with a molecular weight of 792.

[Production of one-shot curing film F1]

Each film-forming composition obtained in the examples and comparative examples was applied to a polypropylene (PP) plate using a bar coater so that the resin film thickness was 60 μm, and then heat-cured at 90°C for 30 minutes. Thereafter, a primary cured film F1 was obtained by peeling it off from the PP plate.

[Production of one-shot curing film F1']

Each film-forming composition obtained in the embodiment and the comparative example was coated on a polypropylene (PP) plate using a bar coater in such a manner that the resin film thickness became 60 μm, and then heat-cured at 140°C for 30 minutes. Thereafter, a primary cured film F1' was obtained by peeling it off from the PP plate.

[Comment 1] Extensibility (1) Determination of glass transition temperature of thin films

Each film-forming composition obtained in the embodiment and the comparative example was coated on a stainless steel plate using a rod coater in such a manner that the resin film thickness was 25 μm, and then heat-cured at 90°C for 30 minutes to obtain a test piece for measuring the glass transition temperature. The logarithmic attenuation rate of the obtained test piece was measured using a rigid pendulum viscoelastic tester (RPT-3000W manufactured by A&T Co., Ltd.). The peak of the temperature-logarithmic attenuation rate curve was set as the glass transition temperature of the film. The measurement temperature of the elongation at break and the fracture stress was determined based on the glass transition temperature obtained in the measurement.

(2) Determination of elongation at break and fracture stress

The tensile test of each film produced using the film forming composition obtained in the embodiment and the comparative example was carried out under the conditions shown below using a universal testing machine (RTE-1210 manufactured by A&T Co., Ltd.). Based on the elongation at break and the fracture strength obtained in the measurement, the elongation at break and the fracture stress of the film were evaluated according to the following evaluation criteria.

(Measurement conditions)

Specimen size: width 10×length 20mm

Specimen thickness: about 60μm

Stretching speed: 20mm/min

Measuring temperature: measured glass transition temperature + 10℃

(Evaluation criteria for elongation at break)

☆: The elongation at break of the film at the measured temperature is above 200%

◎: The elongation at break of the film at the measured temperature is greater than 180% and less than 199%

○: The elongation at break of the film at the measured temperature is greater than 150% and less than 179%

△: The elongation at break of the film at the measured temperature is greater than 50% and less than 149%

×: The elongation at break of the film at the measured temperature is less than 50%

(Evaluation criteria for fracture stress)

☆: The fracture stress of the film at the measured temperature is above 1.30MPa

◎: The fracture stress of the film at the measured temperature is above 1.10MPa and below 1.29MPa

○: The fracture stress of the film at the measured temperature is above 0.80MPa and below 1.09MPa

△: The fracture stress of the film at the measured temperature is above 0.50MPa and below 0.79MPa

×: The breaking stress of the film at the measured temperature does not reach 0.50MPa

[Evaluation 2] Adhesion resistance

The presence or absence of adhesion of each film produced using the film-forming composition obtained in the embodiment and the comparative example was confirmed by finger contact. The adhesion resistance was evaluated according to the evaluation criteria shown below. In addition, the "adhesion" here refers to the characteristic property of adhesion called instantaneous adhesion, which can be specifically referred to as the electrical resistance when the adhesive object is immediately peeled off after being sandwiched between fingers.

(Evaluation criteria)

○: No adhesion was observed

△: Slight adhesion was observed, but it was not a hindrance in actual use.

×: Obvious adhesion was confirmed

[Production of secondary hardened film] (Use the primary curing film F1 and the secondary curing film F2)

Each film-forming composition obtained in the embodiment and the comparative example was applied to a glass plate using a bar coater in such a manner that the resin film thickness became 60 μm, and then heat-cured at 90°C for 30 minutes to obtain a primary cured film F1.

The obtained primary cured film F1 was further heated and cured at 140°C for 30 minutes to obtain a secondary cured film F2.

(Use the primary curing film F1' and the secondary curing film F2')

Each film-forming composition obtained in the embodiment and the comparative example was applied to a glass plate using a rod coater in such a manner that the resin film thickness became 60 μm, and then heated and cured at 140°C for 30 minutes to obtain a primary cured film F1'.

The surface of the primary cured film F1' was irradiated with ultraviolet light having a cumulative light intensity of 900 mJ/cm ² for 5 minutes, thereby obtaining a secondary cured film F2.

[Evaluation 3] Solvent resistance of thin film laminates

0.1 mL of xylene was dripped onto the surface of each thin film laminate prepared using the thin film forming composition obtained in the embodiment and the comparative example. After that, the state of the film was visually observed after standing for 15 minutes, and the solvent resistance was evaluated. The evaluation criteria are as follows.

(Evaluation criteria)

○: No roughness or marks were found on the surface

△: Slight traces were found on the surface, but they did not cause any problems in actual use.

×: Obvious roughness and marks were confirmed on the surface

[Production of adhesive resin hardened material (laminated polyester flat plate)]

A polyethylene terephthalate sheet manufactured by Takiron (product name: Super PET sheet PET-6010, film thickness: 4mm) was used as the polyester sheet.

The coating liquid containing the adhesive resin composition obtained in the embodiment and the comparative example and adjusting the resin solid content to 30 mass % was applied to the surface of the above-mentioned polyethylene terephthalate flat plate using an applicator and dried at 90°C for 30 seconds. Thereafter, a heat treatment step was performed at 150°C for 1 minute, followed by cooling to obtain an easy-to-bond polyester flat plate having an easy-to-bond layer with a film thickness of 1 μm.

Furthermore, a UV-curable acrylic resin composition having the following composition was applied to the easy-to-attach treatment layer using an applicator, and UV light was irradiated from the side of the flat plate for 5 minutes with a cumulative light intensity of 900 mJ/ ^cm2 . Thereafter, a heat treatment was performed at 150°C for 10 minutes to obtain a laminated polyester flat plate having a UV-curable acrylic resin layer with a thickness of 20 μm.

(Composition of UV-curable acrylic resin composition)

2,2-Bis(4-(acryloyloxydiethoxy)phenyl)propane (produced by Shin-Nakamura Chemical Co., Ltd., product name NK ESTER A-BPE-4): 50% by mass relative to the total mass of the UV-curable acrylic resin composition

‧Tetrahydrofuran methyl acrylate (produced by Osaka Organic Chemical Industry Co., Ltd., product name Viscoat # 150): 40% by mass relative to the total mass of the UV-curable acrylic resin composition

‧(Manufactured by Ciba Specialty Chemical, product name Irgacure184): 10% by mass relative to the total mass of the UV-curable acrylic resin composition

[Evaluation 4] Solvent resistance before layering

A polyethylene terephthalate sheet manufactured by Takiron (product name: Super PET sheet PET-6010, film thickness: 4mm) was used as the polyester sheet.

The coating liquid containing the adhesive resin composition obtained in the embodiment and the comparative example and adjusting the resin solid content to 30 mass % was applied to the surface of the above-mentioned polyethylene terephthalate flat plate using an applicator and dried at 90°C for 30 seconds. Thereafter, a heat treatment step was performed at 150°C for 1 minute, followed by cooling to obtain an easy-to-bond polyester flat plate having an easy-to-bond layer with a film thickness of 1 μm.

Toluene was added to the obtained easy-to-process polyester flat plate, and a watch glass was placed on it and left at 23°C for 2 hours. Afterwards, the toluene was wiped off with a Kimwipe and the coating state was confirmed. The solvent resistance before lamination was evaluated according to the following evaluation criteria.

(Evaluation criteria)

5: Almost no change

4: Traces were faintly observed in a 1cm ring

3: Obtained obvious traces in a 1cm ring

2: Partial degradation is observed inside the 1cm ring

1: Overall deterioration inside the 1cm ring

[Evaluation 5] Adhesion to the upper layer

100 grid-like cuts were cut through the UV-curing acrylic resin layer of the obtained laminated polyester flat plate using a cut-guide with a gap of 2 mm. Then, a cellophane adhesive tape (manufactured by Nichiban, type 405: 24 mm wide) was attached to the grid-like cut surface and rubbed with an eraser to make it completely close. Then, the cellophane adhesive tape was rapidly peeled off from the UV-curing acrylic resin layer of the laminated polyester flat plate at a peeling angle of 180°, and the peeled surface was monitored and the peeled grids were counted. The following evaluation criteria are used to evaluate the closeness with the upper layer.

(Evaluation criteria)

5: The peeled grid is 0

4: Only part of the edge of the grid is peeling off

3: The peeled grid is greater than 1 and less than 10

2: The peeled grid is above 11 and below 20

1: The peeled grid is 21 or above

[Rating 6] Stability under high temperature and high humidity

The obtained laminated polyester plate was placed in a high temperature and high humidity tank at 80°C and 95% RH for 48 hours. Afterwards, the laminated polyester plate was taken out and placed at room temperature for 10 hours. Afterwards, the adhesion was evaluated in the same way as the initial adhesion evaluation. The evaluation criteria are as follows.

(Evaluation criteria)

5: The peeled grid is 0 (including the case where only the edge is peeled)

4: The peeled grid is greater than 1 and less than 15

3: The peeled grid is above 16 and below 30

2: The peeled grid is above 31 and below 50

1: The peeled grid is 51 or above

[Evaluation of coating film] [Evaluation 7] Low temperature drying

Each coating composition obtained in the examples and comparative examples was applied to a polypropylene plate, and the coating film was cut after being calcined at 120°C for 30 minutes and placed in acetone at 23°C for 24 hours. The coating film after immersion was dried, and the percentage of the remaining coating film was calculated based on the weight before acetone immersion, and the residual rate was evaluated. The evaluation criteria are as follows.

(Evaluation criteria)

◎: The residual rate is more than 90%

○: The residual rate is 80% or more and less than 90%

×: The residual rate is less than 80%

[Evaluation 8] Solvent resistance of coating

Each coating composition obtained in the examples and comparative examples was applied to a glass plate, and after being fired at 120°C for 30 minutes, it was left to stand for 24 hours in an environment of 23°C and 50% humidity. The coating was subjected to a friction test in which a cotton cloth soaked in acetone was moved back and forth 20 times, and the appearance of the coating was visually observed and evaluated. The evaluation criteria are as follows.

(Evaluation criteria)

◎: The coating has hardly changed

○: Slight traces of coating appear

×: Dissolution traces appear on the coating

[Evaluation 9] Trial period of paint

The viscosity increase rate at 25°C when the initial viscosity of each coating composition obtained in the embodiment and comparative example after being stored at 23°C for 7 hours was set as 100% was evaluated. The evaluation criteria are as follows.

(Evaluation criteria)

◎: The viscosity increase rate is 100% or more and less than 150%

○: The viscosity increase rate is 150% or more and less than 180%

△: The viscosity increase rate is 180% or more and less than 200%

×: Viscosity increase rate is more than 200%

<Synthesis of polyisocyanate> [Synthesis Example 1] (Synthesis of polyisocyanate p-1)

A four-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen blowing tube, and dropping funnel was set to a nitrogen atmosphere, and 600 parts of HDI and 30 parts of polyester polyol derived from triol and ε-caprolactone (manufactured by Daicel Co., Ltd., trade name "Placcel 303") were added. The temperature in the reactor was set to 90°C and maintained for 1 hour under stirring to carry out the urethanization reaction. Thereafter, the temperature in the reactor was maintained at 60°C, and tetramethylammonium octanoate, an isocyanurate catalyst, was added. When a specific yield was reached, phosphoric acid was added to stop the reaction. After filtering the reaction solution, unreacted HDI was removed using a thin film evaporator. The number average molecular weight of the reaction product was measured by GPC, and the isocyanate content was measured by titration to confirm the formation of polyisocyanate. The viscosity of the obtained polyisocyanate p-1 at 25°C was 9,500mPa‧s, the isocyanate content was 19.2%, the number average molecular weight was 1,100, and the average isocyanate base number was 5.3.

[Synthesis Example 2] (Synthesis of polyisocyanate p-2)

A four-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen blowing tube, and dropping funnel was set to a nitrogen atmosphere. After adding 600 parts of HDI, the temperature in the reactor was maintained at 60°C. The isocyanurate-forming catalyst tetramethylammonium octanoate was added. When the isocyanate content of the reaction solution reached 38.7% by mass, phosphoric acid was added to stop the reaction. After filtering the reaction solution, unreacted HDI was removed using a thin film evaporator. The number average molecular weight of the reaction product was measured by GPC, and the isocyanate content was measured by titration to confirm the formation of polyisocyanate. The viscosity of the obtained polyisocyanate p-2 at 25°C is 2,700mPa‧s, the isocyanate content is 21.7%, the number average molecular weight is 660, and the average isocyanate group number is 3.4.

[Synthesis Example 3] (Synthesis of polyisocyanate p-3)

A four-necked flask equipped with a stirrer, thermometer, reflux condenser, nitrogen blowing tube, and dropping funnel was set to a nitrogen atmosphere, and 700 parts of HDI, 300 parts of IPDI, and 30 parts of polycaprolactone polyol-based polyester polyol "Placcel 303" (Daicel Chemical's trade name, molecular weight 300) as a triol were added. The temperature in the reactor was kept at 90°C for 1 hour under stirring to carry out the urethanization reaction. Thereafter, the temperature in the reactor was kept at 80°C, and tetramethylammonium octanoate, an isocyanurate catalyst, was added. When the isocyanate content of the reaction solution reached 36.2% by mass, phosphoric acid was added to stop the reaction. After filtering the reaction solution, unreacted HDI was removed using a thin film evaporator. The number average molecular weight of the reaction product was determined by GPC, and the isocyanate content was determined by titration to confirm the formation of polyisocyanate. The viscosity of the obtained polyisocyanate p-3 at 25°C was 180,000mPa‧s, the isocyanate content was 18.7%, the number average molecular weight was 1200, and the average isocyanate base number was 5.3.

[Synthesis Example 4] (Synthesis of polyisocyanate p-4)

A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen blowing tube, and a dropping funnel was set to a nitrogen environment, and 1000 parts of HDI and 340 parts of a polyester polyol derived from triol and ε-caprolactone (manufactured by Daicel Co., Ltd., trade name "Placcel 308") were added. The temperature in the reactor was maintained at 95°C for 1.5 hours under stirring to carry out the urethanization reaction. After filtering the reaction solution, the unreacted HDI was removed using a thin film evaporator. The number average molecular weight of the reaction product was measured by GPC, and the isocyanate content was measured by titration to confirm the formation of polyisocyanate. The viscosity of the obtained polyisocyanate p-4 at 25°C is 4,000mPa‧s, the isocyanate content is 9.1%, the number average molecular weight is 1,500, and the average isocyanate group number is 3.2.

<(1-1) Production of polyisocyanate compositions> [Implementation Example 1-1-5] (Manufacturing of polyisocyanate composition PI-a1-1)

A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen blowing tube, and a dropping funnel was set to a nitrogen environment, 500 g of polyisocyanate p-1 obtained in Synthesis Example 1 and 200 g of butyl acetate were added, heated to 60°C while stirring, and 0.75 times the molar amount of 3,5-dimethylpyrazole (hereinafter referred to as "3,5-DMP") as a capping agent was slowly added relative to the molar number of isocyanate groups in polyisocyanate p-1. After all the additions were made, stirring was continued for 1 hour to obtain a polyisocyanate composition PI-a1-1.

[Comparison Example 1-3-1] (Manufacturing of polyisocyanate composition PI-b1-1)

The polyisocyanate p-1 synthesized in Synthesis Example 1 was diluted with butyl acetate in such a manner that the solid content was 75% by mass relative to the total mass of the composition, thereby obtaining a polyisocyanate composition PI-b1-1.

[Comparison Example 1-3-2] (Manufacturing of polyisocyanate composition PI-b1-2)

The addition amount of 3,5-dimethylpyrazole was set to 1.05 times the molar amount of the isocyanate group of the polyisocyanate. In addition, the same method as Example 1 was used to obtain the polyisocyanate composition PI-b1-2.

[Implementation Example 1-1-3] (Manufacturing of polyisocyanate composition PI-a1-3)

The polyisocyanate composition PI-b1-1 obtained in Comparative Example 1-3-1 and the polyisocyanate composition PI-b1-2 obtained in Comparative Example 1-3-2 were mixed at an isocyanate molar ratio of 1:1 (including blocked isocyanate groups) to obtain a polyisocyanate composition PI-a1-3.

[Implementation Examples 1-1-1, 1-1-2, 1-1-4, 1-1-6~1-1-11] (Polyisocyanate compositions PI-a1-1, PI-a1-2, PI-a1-4, PI-a1-6~PI-a1-11)

The types of polyisocyanate and blocking agent used, the blocking rate, and the content of partially blocked polyisocyanate (molar %) are set as shown in Table 1-2. In addition, the same method as Example 1-1-5 is used to obtain polyisocyanate compositions PI-a1-1, PI-a1-2, PI-a1-4, PI-a1-6 to PI-a1-11. In addition, in Table 1-2, "3,5-DMP" is 3,5-dimethylpyrazole, "MEK-Ox" is methyl ethyl ketone oxime, "ε-CL" is ε-caprolactam, and "DEM" is diethyl malonate (the same applies below).

<(1-2) Production of thin film forming composition> (Preparation of active hydrogen-containing compounds AH-1-1~AH-1-5)

Prepare ethyl acetate solutions of acrylic polyol resin (AP), polycaprolactone diol resin (PCL-1, PCL-2), and polycarbonate diol resin (PCD). The hydroxyl concentration (resin basis), solid content, and solvents used of these resins are shown in Tables 1-3.

The above resins are mixed in the ratios listed in Table 1-4 to obtain active hydrogen-containing compounds AH1-1~AH1-5.

[Table 1-3]

[Implementation Example 1-2-1] (Manufacturing of film-forming composition F-a1)

For the polyisocyanate composition PI-a1-3 obtained in Example 1-1-3, the active hydrogen-containing compound AH-1-1 was prepared in such a way that NCO/OH=1.0, and diluted with propylene glycol-1-monomethyl ether-2-acetate (PMA) to a solid content of 25% by mass. At this time, dibutyltin dilaurate was added in such a way that the relative resin concentration was 0.1%, and a film-forming composition F-a1 was obtained.

[Implementation Examples 1-2-2~1-2-15] (Manufacturing of thin film forming compositions F-a2~F-a15)

The active hydrogen-containing compound and the polyisocyanate composition are set as shown in Table 1-5. In addition, the same method as Example 1-2-1 is used to obtain the film-forming composition F-a2~F-a15.

[Comparison Example 1-4-1] (Manufacturing of film-forming composition F-b1)

The film-forming composition was obtained by the same method as in Example 1-2-2 except that the polyisocyanate composition PI-b1-1 obtained in Comparative Example 1-3-1 was used as the polyisocyanate composition.

[Comparison Example 1-4-2] (Manufacturing of film-forming composition F-b2)

The polyisocyanate composition PI-b1-2 obtained in Comparative Example 1-3-2 was used as the polyisocyanate composition, and the film-forming composition F-b2 was obtained by the same method as in Example 1-2-2.

<(1-3) Manufacturing of primary curing film F1 and secondary curing film F2>

The above-mentioned method for preparing the primary cured film F1 and the method for preparing the film laminate using the primary cured film F1 were used, and the film forming composition prepared in the embodiment and the comparative example was used to prepare the primary cured film F1 and the secondary cured film F2, and the film was evaluated. The evaluation results are shown in the following Table 1-5. Among them, the film using the film forming composition F-b2 prepared in the comparative example 1-4-2 was brittle and it was impossible to cut out the test piece for measuring the elongation at break and the fracture stress. Therefore, it is recorded as "unable to measure" in Table 1-5.

According to Table 1-5, the films using the film-forming compositions F-a1 to F-a15 of Examples 1-2-1 to 1-2-15 maintain good elongation and have excellent anti-blocking properties. In addition, the film laminate having the film laminated on a glass plate has excellent solvent resistance.

The film using the film-forming compositions F-a2, F-a5~F-a15 containing a polyisocyanate composition with a relatively high blocking rate tends to have particularly good elongation at break.

In addition, the films of the film-forming compositions F-a2, F-a5~F-a7, F-a9~F-a15, which contain a polyisocyanate composition with a blocking rate of 50~80 mol% and a functional group X of the primary cured film with a molar number γ of 0.1 or more and 0.4 or less, tend to have particularly good elongation at break and stress at break.

On the other hand, among the films and film laminates using the film-forming compositions F-b1 to F-b2 of Comparative Examples 1-4-1 and 1-4-2, it was not possible to obtain films that maintained good elongation and had excellent anti-blocking and solvent resistance.

<(1-4) Production of film-forming composition and primary curing film F1'> [Implementation Example 1'-2-1~1'-2-2] (Manufacturing of film-forming composition F'-a1)

For the polyisocyanate composition PI-b1-1, a polyester acrylate PEA-1 containing a hydroxyl group (hydroxyl concentration 1.21 mass%, acryl concentration 11.0 mass%) was prepared in such a way that NCO/OH=1.0. Then, a photoinitiator Omnirad 651 (manufactured by IGM Resin) was added in such a way that it became 5 mass% relative to PEA-1. Furthermore, propylene glycol-1-monomethyl ether-2-acetate (PMA) was used to dilute it to a solid content of 25 mass%. At this time, dibutyltin dilaurate was added in such a way that it became 0.1% relative to the resin concentration to obtain a film-forming composition F'-a1.

(Manufacturing of film-forming composition F'-a2)

The film-forming composition F'-a2 was obtained by the same method as F'-a1 except that the polyester acrylate containing hydroxyl groups was changed to PEA-2 (hydroxyl group concentration 2.12 mass %, acryl group concentration 20.6 mass %).

According to the above-mentioned method for preparing the primary cured film F1' and the method for preparing a thin film laminate using the primary cured film F1', the primary cured film F1' and the secondary cured film F2' were prepared using the thin film forming composition prepared in the embodiment and the comparative example, and the film was evaluated. The evaluation results are shown in Table 1-6.

According to Table 1-6, the films formed using the film-forming compositions F-b1 to F-b4 of Examples 1-3-1 to 1-3-2 maintain good elongation and have excellent anti-blocking properties. In addition, the film laminate formed by laminating the film on a glass plate has excellent solvent resistance.

<(2-1) Production of polyisocyanate compositions> [Implementation Example 2-1-1] (Manufacturing of polyisocyanate composition PI-a2-1)

A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen blowing tube, and a dropping funnel was set to a nitrogen environment, 500 g of polyisocyanate p-1 obtained in Synthesis Example 1 and 200 g of butyl acetate were added, heated to 60°C while stirring, and 0.75 times the molar amount of 3,5-dimethylpyrazole (hereinafter referred to as "3,5-DMP") as a capping agent was slowly added relative to the molar number of isocyanate groups in polyisocyanate p-1. After all the additions were made, stirring was continued for 1 hour to obtain a polyisocyanate composition PI-a2-1.

[Comparison Example 2-3-1] (Manufacturing of polyisocyanate composition PI-b2-1)

The polyisocyanate p-1 synthesized in Synthesis Example 1 was diluted with butyl acetate in such a manner that the solid content was 75% by mass relative to the total mass of the composition, thereby obtaining a polyisocyanate composition PI-b2-1.

[Comparison Example 2-3-2] (Manufacturing of polyisocyanate composition PI-b2-2)

The addition amount of 3,5-dimethylpyrazole was set to 1.05 times the molar amount of the isocyanate group of the polyisocyanate. In addition, the polyisocyanate composition PI-b2-2 was obtained using the same method as Example 1.

[Comparison Example 2-3-3] (Manufacturing of polyisocyanate composition PI-b2-3)

A mixture of MEK-Ox and 3,5-DMP (MEK-Ox/3,5-DMP=1/1 (molar ratio)) was used to replace 3,5-dimethylpyrazole, and the amount added was set to 1.05 times the molar number of the isocyanate group of the polyisocyanate. In addition, the polyisocyanate composition PI-b2-3 was obtained using the same method as Example 1.

[Implementation Example 2-1-2] (Manufacturing of polyisocyanate composition PI-a2-2)

The polyisocyanate composition PI-b2-1 obtained in Comparative Example 2-3-1 and the polyisocyanate composition PI-b2-2 obtained in Comparative Example 2-3-2 were mixed at an isocyanate molar ratio of 1:1 (including blocked isocyanate groups) to obtain a polyisocyanate composition PI-a2-2.

[Implementation Examples 2-1-3~2-1-11] (Manufacturing of polyisocyanate compositions PI-a2-3~PI-a2-11)

The types of polyisocyanate and blocking agent used, the blocking rate, and the content (molar %) of partially blocked polyisocyanate are set as shown in Table 2-1. In addition, the same method as Example 1 is used to obtain polyisocyanate compositions PI-a2-3 to PI-a2-11. In Table 2-1, "MEK-Ox" is methyl ethyl ketone oxime, and "ε-CL" is ε-caprolactam (the same applies below).

<(2-2) Production of adhesive resin composition> [Implementation Example 2-2-1] (Manufacturing of adhesive resin composition S-a1)

For the polyisocyanate composition PI-a2-1 obtained in Example 2-1-1, an ethyl acetate solution of an acrylic polyol resin (hydroxyl concentration 4.5 mass% (resin basis), resin solid content 41 mass%, hereinafter referred to as "AH-3") was prepared in a manner such that NCO/OH=1.0, and diluted with propylene glycol-1-monomethyl ether-2-acetate (PMA) to a solid content of 30 mass%, to obtain an adhesive resin composition S-a1.

[Implementation Examples 2-2-2~2-2-11 and Comparative Examples 2-4-1~2-4-3] (Adhesive resin compositions S-a2~S-a11 and S-b1~S-b3)

Assuming that the type of polyisocyanate composition is as listed in Table 2-2, the same method as in Example 2-2-1 is used to obtain adhesive resin compositions S-a2~S-a11 and S-b1~S-b3.

The above method was used to evaluate the adhesive resin compositions produced in the examples and comparative examples. The results are shown in the following Table 2-2.

According to Table 2-2, the adhesive resin cured products using adhesive resin compositions S-a1~S-a10 (Examples 2-2-1~2-2-11) have excellent solvent resistance before lamination, adhesion to the upper layer, and stability under high temperature and high humidity.

In the adhesive resin compositions S-a1 and S-a4 (Examples 2-2-1 and 2-2-4), S-a3 and S-a6 (Examples 2-2-3 and 2-2-6), the obtained The adhesive resin cured product of the present invention tends to have better adhesion to the upper layer and better stability under high temperature and high humidity. On the other hand, the adhesive resin compositions S-a1 and S-a3 (Examples 2-2-1 and 2-2-3) containing polyisocyanate compositions with relatively low end-capping rates tend to have better solvent resistance before lamination when preparing the adhesive resin cured product.

In addition, among the adhesive resin compositions S-a2 and S-a5 (Examples 2-2-2 and 2-2-5), the adhesive resin composition S-a5 (Example 2-2-5) containing a relatively high content of partially blocked polyisocyanate has a tendency to have better solvent resistance before lamination, adhesion to the upper layer, and stability under high temperature and high humidity when the adhesive resin cured product is made.

Furthermore, among the adhesive resin compositions S-a5, S-a8 to S-a10 (Examples 2-2-5, 2-2-8 to 2-2-10), the adhesive resin compositions S-a5 and S-a9 (Examples 2-2-5 and 2-2-9) containing a polyisocyanate composition having a relatively large total average number of isocyanate groups tend to have better stability under high temperature and high humidity.

Furthermore, among the adhesive resin compositions S-a5, S-a7 and S-a11 (Examples 2-2-5, 2-2-7 and 2-2-11), the adhesive resin composition S-a5 (Example 2-2-5) containing a polyisocyanate composition using 3,5-DMP as a capping agent tends to have better adhesion to the upper layer than the other two examples.

On the other hand, the adhesive resin cured product using adhesive resin compositions S-b1~S-b3 (Comparison Examples 2-4-1~2-4-2) failed to achieve excellent solvent resistance before lamination, adhesion to the upper layer, and stability under high temperature and high humidity.

<(3-1) Production of polyisocyanate composition> [Implementation Example 3-1-1] (Manufacturing of polyisocyanate composition PI-a3-1)

A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen blowing tube, and a dropping funnel was set to a nitrogen environment, 500 g of polyisocyanate p-1 obtained in Synthesis Example 1 and 200 g of butyl acetate were added, heated to 60°C while stirring, and 0.75 times the molar amount of 3,5-dimethylpyrazole (hereinafter referred to as "3,5-DMP") as a capping agent was slowly added relative to the molar number of isocyanate groups in polyisocyanate p-1. After all the additions were made, stirring was continued for 1 hour to obtain a polyisocyanate composition PI-a3-1.

[Comparison Example 3-3-1] (Manufacturing of polyisocyanate composition PI-b3-1)

The polyisocyanate p-2 synthesized in Synthesis Example 2 was diluted with butyl acetate in such a manner that the solid content was 75% by mass relative to the total mass of the composition, thereby obtaining a polyisocyanate composition PI-b3-1.

[Comparison Example 3-3-2] (Manufacturing of polyisocyanate composition PI-b3-2)

The addition amount of 3,5-dimethylpyrazole was set to 1.05 times the molar amount of the isocyanate group of the polyisocyanate. In addition, the polyisocyanate composition PI-b3-2 was obtained using the same method as Example 1.

[Comparison Example 3-3-3] (Manufacturing of polyisocyanate composition PI-b3-3)

A mixture of MEK-Ox and 3,5-DMP (MEK-Ox/3,5-DMP=1/1 (molar ratio)) was used to replace 3,5-dimethylpyrazole, and the added amount was set to 1.05 times the molar number of the isocyanate group of the polyisocyanate. In addition, the polyisocyanate composition PI-b3-3 was obtained using the same method as Example 3-1-1.

[Implementation Example 3-1-12] (Manufacturing of polyisocyanate composition PI-a3-12)

The polyisocyanate composition PI-b3-1 obtained in Comparative Example 3-3-1 and the polyisocyanate composition PI-b3-2 obtained in Comparative Example 3-3-2 were mixed at an isocyanate molar ratio of 2:1 (including blocked isocyanate groups) to obtain a polyisocyanate composition PI-a3-12.

[Implementation Examples 3-1-2~3-1-11] (Manufacturing of polyisocyanate compositions PI-a3-2~PI-a3-11)

The types of polyisocyanate and blocking agent used, the blocking rate, and the content (molar %) of partially blocked polyisocyanate are set as shown in Table 3-1. In addition, the same method as Example 1 is used to obtain polyisocyanate compositions PI-a3-2 to PI-a3-11.

<(3-2) Production of coating compositions> [Implementation Example 3-2-1] (Manufacturing of coating composition C-a1)

For the polyisocyanate composition PI-a3-1 obtained in Example 3-1-1, a solvent naphtha solution of acrylic polyol resin (hydroxyl concentration 4.5 mass% (resin basis), resin solid content 65 mass%, hereinafter referred to as "AH-4") was prepared in a manner such that NCO/OH=1.0, and diluted with butyl acetate to a solid content of 50 mass%, to obtain a coating composition C-a1.

[Implementation Examples 3-2-2~3-2-12 and Comparative Examples 3-4-1~3-4-3] (Coating compositions C-a2~C-a12 and C-b1~C-b3)

Assuming that the type of polyisocyanate composition is as listed in Table 3-2, the coating compositions C-a2~C-a12 and C-b1~C-b3 are obtained by the same method as in Example 3-2-1.

The coating compositions produced in the examples and comparative examples were evaluated using the above method. The results are shown in the following Table 3-2.

According to Table 3-2, the coating compositions using coating compositions C-a1 to C-a12 (Examples 3-2-1 to 3-2-12) have excellent low-temperature drying properties, solvent resistance, and coating test period.

In the coating compositions C-a1, C-a4, C-a5, and C-a6 (Examples 3-2-1, 3-2-4, 3-2-5, and 3-2-6), the coating compositions containing the polyisocyanate composition with a relatively high blocking rate tend to have a longer test period of the coating, while the coating compositions containing the polyisocyanate composition with a relatively low blocking rate tend to have a longer test period of the coating. Among the coating compositions C-a3, C-a7, C-a8, C-a9, C-a10, C-a11, and C-a12 (Examples 3-2-3, 3-2-7, 3-2-8, 3-2-9, 3-2-10, 3-2-11, and 3-2-12) of the acid ester composition, the coating composition tends to have better low-temperature drying properties.

Furthermore, among the coating compositions C-a2, C-a3, C-a6, C-a7, C-a10, and C-a11 (Examples 3-2-2, 3-2-3, 3-2-6, 3-2-7, 3-2-10, and 3-2-11), the coating compositions containing the polyisocyanate composition having a relatively lower content of partially blocked polyisocyanate than the medium level tend to have a better solvent resistance of the obtained coating cured product.

Furthermore, among the coating compositions C-a7 and C-a12 (Examples 3-2-7 and 3-2-12), the coating composition C-a7 (Example 3-2-7) containing a polyisocyanate composition having the same blocking rate but a higher ratio of partially blocked polyisocyanate tends to have a higher trial period of the coating.

On the other hand, the cured coatings using coating compositions C-b1~C-b3 (Comparison Examples 3-4-1~3-4-3) failed to achieve excellent low-temperature drying properties of the coating, solvent resistance of the coating, and the test period of the coating.

[Industrial availability]

According to the polyisocyanate composition of this embodiment, the following polyisocyanate composition can be obtained, which, when used as a film-forming composition, well maintains the elongation of the film and has excellent anti-blocking and solvent resistance, and when used as an adhesive resin composition, has excellent solvent resistance before lamination, and excellent adhesion of various functional layers used as the upper layer and stability under high temperature and high humidity, and when used as a coating composition, can take into account both the solvent resistance of the coating film and the service life of the coating. According to the film-forming composition of this embodiment, a film that well maintains elongation and has excellent anti-blocking and solvent resistance can be provided. The film and film laminate of this embodiment can be made using the above-mentioned film-forming composition, and can be used as a decorative film that can be applied to articles of various materials. The adhesive resin composition and adhesive resin cured product of this embodiment can be made using the above-mentioned polyisocyanate composition, and can provide an adhesive resin cured product with excellent solvent resistance before lamination, excellent adhesion to various functional layers used as the upper layer, and excellent stability under high temperature and high humidity. According to the coating composition and coating cured product of this embodiment, a coating film with excellent solvent resistance and good coating trial period can be provided.

Claims (12)

A one-time curing film is formed by curing a polyisocyanate composition having at least one isocyanate compound selected from the group consisting of aliphatic isocyanates and alicyclic isocyanates as a skeleton and a compound containing active hydrogen, and the film comprises at least one functional group X selected from the group consisting of urethane groups, urea groups, and amide groups generated by curing the above-mentioned compound containing active hydrogen and the above-mentioned polyisocyanate composition, an active hydrogen group, and isocyanate groups blocked by a blocking agent, wherein the above-mentioned active hydrogen-containing compound comprises acrylic polyol, the average total number of isocyanate groups blocked by a blocking agent and isocyanate groups not blocked by a blocking agent in each molecule of polyisocyanate is 3 or more, and 1 mol% or more and 90 mol% or less of the isocyanate groups in the above-mentioned polyisocyanate composition are blocked by a blocking agent, and the above-mentioned blocking agent is an amide compound, an oxime compound or a pyrazole compound. The once-cured film of claim 1, wherein the ratio of the molar number γ of the functional group X contained in the once-cured film to the molar number β of the isocyanate group blocked by the blocking agent, i.e., γ/β, is greater than 0.1 and less than 9.0. As in claim 1, the once-cured film, wherein the molar number γ of the functional group X contained in 1 kg of the once-cured film is greater than 0.05 and less than 1.0. As in claim 2, the once-cured film, wherein the molar number γ of the functional group X contained in 1 kg of the once-cured film is greater than 0.05 and less than 1.0. The once-cured film of claim 1, wherein the molar number γ of the functional group X contained in 1 kg of the once-cured film is greater than 0.1 and less than 0.4. A one-time curing film as claimed in any one of claims 1 to 5, wherein the above-mentioned active hydrogen-containing compound comprises a diol. A secondary hardened film, which is formed by further heating the primary hardened film as in any one of claims 1 to 6 to harden it. A method for manufacturing a secondary hardened film, comprising the following steps: heating the primary hardened film of any one of claims 1 to 6 at a temperature of 50°C or higher and 140°C or lower, and making it follow the formed body and adhere to the formed body; and then heating at a temperature of 50°C or higher and 180°C or lower to harden the attached resin composition. A method for manufacturing a secondary cured film as claimed in claim 8, wherein the ratio γ/γ' of the molar number γ of the functional group X contained in the primary cured film to the molar number γ' of the functional group X contained in the secondary cured film is greater than 0.1 and less than 0.9. A method for manufacturing a secondary cured film as claimed in claim 8 or 9, wherein the molar number γ of the functional group X contained in 1 kg of the primary cured film is greater than 0.05 and less than 1.0, and the molar number γ' of the functional group X contained in 1 kg of the secondary cured film is greater than 0.5 and less than 10. A method for using a once-cured film, comprising the following steps: heating the once-cured film as in any one of claims 1 to 6 at a temperature of 50°C or higher and 140°C or lower, and making it follow a molded body and adhere to the molded body; and then heating at a temperature of 50°C or higher and 180°C or lower to cure the attached resin composition. An article protected by a film, comprising a primary hardening film as in any one of claims 1 to 6 or a secondary hardening film as in claim 7.